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Chiral Diamine-Based Reduction and Oxidation Catalysts
by
Ari Cuperfain
A thesis submitted in conformity with the requirements for the degree of Master of Science
Department of Chemistry University of Toronto
© Copyright by Ari Cuperfain 2014
ii
Chiral Diamine-Based Reduction and Oxidation Catalysts
Ari Cuperfain
Master of Science
Department of Chemistry University of Toronto
2014
Abstract
Asymmetric catalysis remains one of the most significant ways for introducing chirality into
prochiral molecules. There is much interest in elucidating mechanistic details and optimizing
conditions for preexisting systems. Using a combination of experimental and computational
methods, we separately explored two reactions: asymmetric transfer hydrogenation and alkene
epoxidation. For the diamine-based hydrogenation catalyst, a series of diphenylethylenediamine
derivatives were synthesized and used to test the electronic effect of diamine ligands on the rate
of hydrogenation. Contrary to previous findings, we report virtually no difference in catalytic
activity between the various ligands. Computational analysis consolidates our results. For the
manganese-salen catalyzed epoxidation, we present an original mechanism to explain the
observed stereoselectivity. Instead of the traditional “side-on approach”, we propose that
epoxidation proceeds through a planar transition state with sp2 hybridized manganese-oxo
oxygen. This model correctly predicts the sense and degree of stereoselectivity for a number of
catalyst and substrate systems.
iii
Acknowledgments
First and foremost, I would like to thank my supervisor, Dr. Jik Chin, for all of his support and
guidance. He is truly the best supervisor a student could possibly hope for. I have learned much
from him about science, business and the world. Thank you as well to the external reviewer of
this thesis, along with the entire University of Toronto Department of Chemistry faculty and staff
for fostering an academic environment of intellectual curiosity and cutting-edge research.
I would also like to thank my fellow group members, Jon Lau and Kimia Moozeh, for all of their
support. I am grateful for all our time together, and our numerous discussions (both chemistry
and otherwise). As we all graduate this year, I wish them luck and success in their future careers.
I would like to express a special thank you to Dr. Soon Mog So for all of his help in the lab. This
research would not have been possible without him.
On that note, I wish to thank all of the NMR staff including Darcy, Dmitry and Joel for keeping
the facilities running smoothly and always being there – even on weekends – to help with any
troubleshooting issues. Big thanks as well to all the Chem Store workers, especially Ken, Giordi,
and Jim, for making Chem Store the most amusing place in the entire Department. Thank you
also, Giordi, for collecting my NMR tubes every morning.
Lastly, and most importantly, I would like to thank my wonderful friends and family. To my
friends – both in and out of the department – thank you for always being there for me and having
my back. I know we will continue to rely on each other wherever life takes us. And to my family,
there are no words to express how thankful I am to have you all. It was definitely nice to be back
home this year after living abroad for university. I love you guys!
iv
Table of Contents
Acknowledgments .......................................................................................................................... iii
Table of Contents ........................................................................................................................... iv
List of Tables ................................................................................................................................. vi
List of Figures ............................................................................................................................... vii
List of Appendices ........................................................................................................................ xii
Chapter 1 Electronic Effects on Asymmetric Transfer Hydrogenation Reactivity ........................ 1
1.1 Introduction ......................................................................................................................... 1
1.1.1 Chiral Diamines in Catalysis .................................................................................. 1
1.1.2 Asymmetric Transfer Hydrogenation and the Noyori Catalyst .............................. 3
1.1.3 Synthetic Applications of Resonance Assisted Hydrogen Bonds ........................... 7
1.2 Research Goals .................................................................................................................... 9
1.3 Results and Discussions ...................................................................................................... 9
1.3.1 Synthesis of Monotosylated Daughter Diamine Derivatives as Catalyst Precursors ................................................................................................................ 9
1.3.2 Technique for Monitoring Hydrogenation Kinetics ............................................. 12
1.3.3 Electronic Effect of Monotosylated Diamine Substituents on Catalytic Activity ................................................................................................................. 13
1.3.4 Computational Studies .......................................................................................... 15
1.3.5 Contribution of Resonance Assisted Hydrogen Bonding Towards Rate of Hydrogenation ....................................................................................................... 18
1.4 Conclusions and Future Work .......................................................................................... 20
1.5 Experimental ..................................................................................................................... 20
1.5.1 General Considerations ......................................................................................... 20
1.5.2 General Procedure for Daughter Diamine Synthesis ............................................ 21
1.5.3 General Procedure for Monotosylation of Daughter Diamines ............................ 22
1.5.4 General Procedure for Asymmetric Transfer Hydrogenation Reactions .............. 22
v
1.5.5 Energy Calculations For Catalysts, Reaction Intermediates and Transition States ..................................................................................................................... 24
1.5.6 Characterization Data ............................................................................................ 27
Chapter 2 The Origin of Stereoselectivity in the Jacobsen-Katsuki Epoxidation ........................ 32
2.1 Introduction ....................................................................................................................... 32
2.1.1 Structural Considerations of the Jacobsen-Katsuki Epoxidation Catalyst With Respect to Stereoselectivity .................................................................................. 32
2.1.2 The Mechanism of Manganese-salen Catalyzed Epoxidation .............................. 36
2.1.3 The Nature of the Manganese-Oxide Bond and the Active Catalytic Species ..... 39
2.2 Research Goals .................................................................................................................. 40
2.3 Results and Discussion ..................................................................................................... 41
2.3.1 Challenges With the Prevailing Model ................................................................. 41
2.3.2 Agreement of Computational Modeling with Experimental Observations .......... 45
2.3.3 Advantages Offered By Considering A Planar Transition State .......................... 51
2.3.4 The Hybridization of the Axial Oxygen Ligand ................................................... 56
2.4 Conclusions and Future Work .......................................................................................... 59
2.5 Experimental ..................................................................................................................... 60
2.5.1 General Considerations ......................................................................................... 60
2.5.2 Energy Calculations On Bent Geometry Transition State Analogs ...................... 60
2.5.3 Energy Calculations for Different Quadrants ....................................................... 63
2.5.4 Energy Calculations on Planar Geometry Transition States ................................. 64
2.5.5 Alignment of Crystal Structure with Computed Structure ................................... 67
2.5.6 Energy Calculations on Manganese-Oxo Hybridization ...................................... 68
2.5.6 Calculation of Predicted Enantiomeric Excess ..................................................... 68
References ..................................................................................................................................... 70
Appendix A: 1H and 13C NMR Spectra ........................................................................................ 74
Appendix B: Cartesian Coordinates of Computed Complexes…………………………………..82
vi
List of Tables
Table 1.1: Synthesis of substituted diimines. ................................................................................ 10
Table 1.2: Synthesis of substituted diamine hydrochloride salts. ................................................. 11
Table 1.3: Synthesis of TsDPEN and other substituted monotosyl diamines. ........................ 12
Table 1.4: Rate of hydrogenation of acetophenone and TOF using variously substituted
monotosylated diamines as ligands ............................................................................................... 14
Table 1.5: Energies for the different species participating in asymmetric transfer hydrogenation
....................................................................................................................................................... 16
Table 2.1: Comparison of literature experimental results with computational prediction for
a variety of catalysts .................................................................................................................... 53
Table 2.2: Comparison of literature experimental results with computational prediction for
a variety of substrates ................................................................................................................. 55
Table 2.3: Relative energies and other computed physical properties of potential (salen)Mn=O
species ........................................................................................................................................... 56
Table 2.4: Calculated energies using DFT B3LYP/6-‐31G* of products and reactants involved
in oxygen transfer epoxidation. ................................................................................................. 58
vii
List of Figures
Figure 1.1: Chiral diamines used in various asymmetric catalysis reactions ................................. 2
Figure 1.2 Chemical structures of the most common chiral diamines used in catalysis, DPEN and
dach ................................................................................................................................................. 3
Figure 1.3: Industrially relevant applications of asymmetric transfer hydrogenation .................... 4
Figure 1.4: Mechanism for ATH using formic acid/triethylamine and aryl alkyl ketone .............. 5
Figure 1.5: Relative activity of monotosyl diamines for ATH in the Johnson Matthey patent ...... 6
Figure 1.6: Resonance assisted hydrogen bonding in β-diketone enols leads to particularly strong
H-bonds ........................................................................................................................................... 7
Figure 1.7: Synthetic applications of resonance assisted hydrogen bonding .................................. 8
Figure 1.8: Mechanism and scheme for the diaza-Cope rearrangement ......................................... 9
Figure 1.9: Relative catalytic activity for a series of substituted monotosylated diamine ligands 14
Figure 1.10: Model structures used for computational analysis of hydrogenation reaction
pathway for variously substituted diamine analogs. ..................................................................... 16
Figure 1.11: Rate of hydrogenation using various substrates ....................................................... 19
Figure 2.1: Jacobsen’s Mn(III) asymmetric epoxidation catalyst ................................................. 32
Figure 2.2: Side-on approach of alkene to the manganese-oxo complex ..................................... 34
Figure 2.3: The salen step, engendered by the absolute stereochemistry of the diamine ............. 35
Figure 2.4: Proposed mechanisms for Mn-catalyzed epoxidation of Z-alkenes ........................... 36
Figure 2.5: Radical clock ring opening of ((Z)-1-((1S,2S)-2-phenylcyclopropyl)prop-1-en-1-
yl)benzene. .................................................................................................................................... 37
Figure 2.6: Corey’s proposed pathway for Jacobson epoxidation of indene ................................ 38
viii
Figure 2.7: Manganese-oxo compound used for the calculation performed by Houk et al. ......... 40
Figure 2.8: Experimental observations and computed relative energies of epoxide enantiomers
bound to the SS-Jacobsen catalyst ................................................................................................. 42
Figure 2.9: Aerial view of alkene approach to manganese-oxo complex as part of the proposed
pathway invoked by Jacobsen to explain the observed sense of stereoselectivity ........................ 43
Figure 2.10: NMR competition reaction between (2R,3S)-‐2-‐phenyl-‐3-‐methylaziridine (4)
with: A) (R,R)-‐3; B) (S,S)-‐3; and C) equal mixture of (S,S)-‐3 and (R,R)-‐3 ................................ 45
Figure 2.11: Computed relative energies of aziridine enantiomers bound to the SS-‐Jacobsen
catalyst ........................................................................................................................................................................ 45
Figure 2.12: Crystal structures of (2R,3S)-‐2-‐phenyl-‐3-‐methylaziridine bound to both
enantiomers of the Jacobsen catalyst. ........................................................................................................... 46
Figure 2.13: a) (R,R)-‐3, with the corresponding cartoon Lewis representation used
throughout. b) Four possible orientations of (2R,3S)-‐2-‐phenyl-‐3-‐methylaziridine bound to
(S,S)-‐3 ........................................................................................................................................... 48
Figure 2.14: Side view (top) and aerial view (bottom) of (2R,3S)-‐4 bound to (S,S)-‐3. Crystal
(left) and computed (right) structures are compared ............................................................. 49
Figure 2.15: Side view (top) and aerial view (bottom) of (2R,3S)-4 bound to (R,R)-3. Crystal
(left) and computed (right) structures are compared ..................................................................... 50
Figure 2.16: Aligned structures of (S,S)-‐3 and (R,R)-‐3 bound to (2R,3S)-‐4 determined by
both X-‐ray crystallography (gray) and molecular modeling computation (red) ................... 51
Figure 2.17: Experimental observations and computed relative energies of epoxide
enantiomers bound to the SS-‐Jacobsen catalyst ....................................................................... 51
Figure 2.18: HOMO and LUMO orbitals of cis-2-butene and the Jacobsen manganese-oxo
catalyst, respectively ..................................................................................................................... 57
ix
List of Abbreviations
δ chemical shift
% v/v percent volume over volume
Å Angstrom
ACDC asymmetric counteranion-directed catalysis
ATH asymmetric transfer hydrogenation
B3LYP Becke, three-parameter, Lee-Yang-Parr
br broad
CD3CN deuterated acetonitrile
CDCl3 deuterated chloroform
conc concentration
d doublet
dach trans-1,2-diaminocyclohexane
DCM dichloromethane
DCR diaza-Cope rearrangement
DFT density functional theory
DMSO dimethyl sulfoxide
DMSO-d6 deuterated dimethyl sulfoxide
DPEN 1,2-diphenylethylenediamine
ee enantiomeric excess
eq equivalent
ESI-MS electrospray ionization-mass spectrometry
Et ethyl
EtOAc ethyl acetate
g grams
H-bonds hydrogen bonds
HKR hydrolytic kinetic resolution
HOMO highest occupied molecular orbital
hpen 1,2-Bis(2-hydroxyphenyl)ethylenediamine
x
hr hour
Hz Hertz
IP intellectual property
J coupling constant
kcal kilocalorie
LUMO lowest unoccupied molecular orbital
M molar
m multiplet
Me methyl
Me-dach 1,2-dimethylcyclohexane-1,2-diamine
mg milligrams
min minutes
MM molecular mechanics
mmol millimoles
MS-MS mass spectrometry-mass spectrometry
NMe2 dimethylamino
NMR nuclear magnetic resonance
OMe methoxy
Ph phenyl
plc public limited company
ppm parts per million
q quartet
RAHB resonance-assisted hydrogen bond
RMSD root mean squared devation
rt room temperature
s singlet; second
S/C substrate-to-catalyst ratio
t triplet
t-Bu tertiary-butyl
THF tetrahydrofuran
TLC thin layer chromatography
TS transition state
xi
Ts Tosyl-
UV Ultraviolet
xii
List of Appendices
Appendix A: 1H and 13C NMR Spectra
Appendix B: Cartesian Coordinates of Computed Complexes
1
Chapter 1 Electronic Effects on Asymmetric Transfer Hydrogenation
Reactivity
1
1.1 Introduction
1.1.1 Chiral Diamines in Catalysis
Chiral 1,2-diamines are a common class of molecules possessing C2-symmetry and are often
used as ligands or as organocatalysts in asymmetric catalysis.1,2 In asymmetric catalysis, chiral
products are synthesized from prochiral reactants in a stereoselective fashion. The catalysts for
these reactions are themselves chiral and can therefore favour the formation of a particular
enantiomer through interaction with the substrate. Since the energies of enantiomers are equal,
there is no thermodynamic preference for forming only one enantiomer; if a chiral compound is
in equilibrium with its enantiomer, a racemic mixture will eventually be reached. Rather,
stereoselectivity is dictated by kinetics and occurs when the barrier of formation is lower for one
enantiomer compared to the other. Thus an effective catalyst for stereoselective reactions must
preferentially accelerate the formation of one enantiomer over the other, while simultaneous
accelerating the reaction sufficiently such that background reactions are insignificant. In other
words, the activation energy for formation of the desired product must be lower than that for the
opposite product, as well as in the absence of the catalyst altogether.3 Chiral diamines have been
shown to facilitate both of these aspects and have been widely successful in synthetic
application.
The reactions in which chiral diamines are employed are diverse. Figure 1.1 shows a series of
widely used catalysts bearing chiral diamine scaffolds, along with the reaction type they
catalyze.
2
N
O
N
O
tButBu
tButBu
Epoxidation/Hydrolysis
M
Ar2P
PAr2
Ru
H2N
NH2Cl
Cl
Hydrogenation
X
X
NP
N O
N
Aldol Reaction
N
H2N
TsRu
Cl
Transfer Hydrogenation
N N
Ph Ph
R
R
Ru
PCy3Cl
Cl
R
Metathesis
N
N
R
X
XPPh3
PdL L
Heck reaction
HNNHO O
PPh2
PPh2
Alkylation
N NH
Ph Ph
PAr2
PAr2
Fe
CO
Cl
Transfer Hydrogenation
N
NR
Ph N
Ph
NP NN
PhPh
N
NR
H
Amination
Pd
Figure 1.1: Chiral diamines used in various asymmetric catalysis reactions. The diamine
scaffold is highlighted in red.
The most commonly used chiral diamines are 1,2-diphenylethylenediamine (DPEN) and trans-
1,2-diaminocyclohexane (dach) (Figure 1.2). This is likely due to a combination of successful
precedents and ease of synthesis and production. Diaminocyclohexanes are produced from the
hydrogenation of 1,2-diaminobenzene, and stereoisomers can be isolated through resolution.
There are a number of known methods for the synthesis of DPEN, many of which are carried out
3
in industrial settings. The most prevalent route remains that developed by Corey;4 the initial
reagents for this method are inexpensive benzil and cyclohexanone.
Figure 1.2 Chemical structures of the most common chiral diamines used in catalysis, DPEN
and dach. Enantiomers not shown.
Two distinct Noyori catalysts are capable of facilitating direct H2 hydrogenation or transfer
hydrogenation, respectively, both of which containing DPEN.5,6 The Jacobson catalyst is derived
from a salen-type ligand bearing a chiral diamine based diimine, which imparts stereoselectivity
to the catalyst.7 Depending on the transition metal and other reaction conditions, the catalyst
could be used in asymmetric olefin epoxidation or epoxide hydrolysis. A similar tetradentate
chiral diamine has been used by Morris to achieve asymmetric transfer hydrogenation using iron
as the metal.8 Grubbs also developed a sterically bulky diamine ruthenium catalyst for
asymmetric ring closing metathesis.9 The Trost ligand also contains dach and can be used for
stereoselective allylic alkylations.10
There are countless other instances of chiral diamines participating in asymmetric catalysis. This
chapter will focus on the role of the diamine ligand in asymmetric transfer hydrogenation with
the Noyori catalyst. The second chapter will look at the origin of stereoselectivity for the
Jacobsen epoxidation catalyst.
1.1.2 Asymmetric Transfer Hydrogenation and the Noyori Catalyst
One of the applications of chiral diamines is in asymmetric transfer hydrogenation (ATH).
Specifically, chiral N-p-Tosyl-1,2-diphenylethylenediamine is used as a ligand for Noyori’s
ATH catalyst (Figure 1.1), and it is this moiety that engenders stereoselectivity during the
reaction.11 ATH remains one of the cornerstone reactions for introducing chiral centres from
prochiral compounds. One of the major advantages of ATH lies in its versatility; both ketones
4
and imines can be hydrogenated, often in excellent yields and stereoselectivities. Indeed, a
number of industrially significant reactions are attainable through Noyori’s ATH (Figure 1.3).12
N
O
NH2O
N
OH
NH2O
oxcarbazepine eslicarbazepine
SOTs
OS
OTs
OHS
O
NH
(S)-duloxetine(Cymbalta)
MeO
OTs
MeO
OTs
HO
HN
OHO OH
OMe
OMedenopamine
O
NBoc
OH
NBoc
NH
O
CF3
(R)-fluoxetine(Prozac)
ClCl
N
ClCl
NH
sertraline
Figure 1.3: Industrially relevant applications of asymmetric transfer hydrogenation.
Noyori’s ATH differs from direct hydrogenation in the nature of the reducing agent. In direct
hydrogenation, molecular hydrogen is used as the hydrogen source.13 In ATH, on the other hand,
a separate donor molecule is used such as formic acid or isopropanol. In the case of formic acid,
5
a hydride is transferred from a formate anion to the ruthenium catalyst, accompanied by
decarboxylation. The mechanism for ATH using formic acid as terminal reducing agent appears
in Figure 1.4. 11,14
RuNTsH2N
Cl
Et3N
Et3N.HCl
RuHN NTs
-H+
+H+Ru
NTsH2N[ ]
CO2
HCOO-
RuNTsH2N
H
Ph
Ph
Ph
Ph Ph
Ph
Ph
Ph
Ar
O
Ar
OH
- Transition State
RuNTsNH
H
PhPh
R
HCO
Ar
Me RuNTsNH
H
PhPh
R
HCO
Me
Ar
favoured TS disfavoured TS
Figure 1.4: Mechanism for ATH using formic acid/triethylamine and aryl alkyl ketone.
There is significant interest of late with regards to using hydrogenation as a means for carbon
dioxide capture. The triple hydrogenation of CO2 to methanol is thermodynamically favourable
and is a potential way to convert waste into fuel by means of the high energy H2 molecule.
Minimizing the global carbon footprint will be a major challenge over the next few years.15
Because cost and energy efficiency in CO2 capture is the most significant current limitation,
hydrogenation catalysts stand to play an important role in overcoming these current barriers. Of
course, none of the derivatives of CO2 are chiral, and the hallmark of Noyori’s hydrogenation
catalyst is its stereoselectivity, but similar catalysts could be employed for efficient CO2
hydrogenation. A number of successful systems for CO2 reduction have been reported in the
literature.16-18
For purposes of CO2 capture, and for more traditional synthetic applications, there is much
interest in developing new hydrogenation catalysts, and in understanding the intricate details of
known hydrogenation pathways. Recent publications have described new and innovative
6
hydrogenation catalysts,19-22 and yet others have used old catalysts towards new applications.23
Others still have probed deeper into the underlying mechanisms of ATH.24-26 Furthermore, a
number of comprehensive reviews have been written on the subject.27,28
Considering the great interest in hydrogenation, and its wide industrial applicability, it is not
surprising that ATH has occupied a significant niche in the intellectual property (IP) portfolio of
many chemical firms. Johnson Matthey plc holds one such patent for the use of substituted
diamine (DPEN) ligands.29 In this patent, Johnson Matthey reported that Ts(pOMe)DPEN was
more active as a ligand than the traditional TsDPEN (Figure 1.5). Using α-tetralone as substrate,
under otherwise identical reaction conditions, the reaction was 70% complete after 5 hours with
Ts(pOMe)DPEN as monotosyl diamine ligand, while only 45% complete after 6 hours with
TsDPEN. This rate-enhancing activity is not obvious; it is important to notice that the aryl rings
are not conjugated with the amine ligand electron donors.
(S,S)-TsDPEN
HNH2N SO
O
MeO OMe(S,S)-Ts(pOMe)DPEN
O OH[RuCl2(p-cymene)]2
(S,S)-TsDPENHCOOH/Et3N
S/C = 50060oC
6 hours 45%98 ee
O OH[RuCl2(p-cymene)]2
(S,S)-Ts(pOMe)DPENHCOOH/Et3N
S/C = 50060oC
5 hours 70%98 ee
HNH2N SO
O
Figure 1.5: Relative activity of monotosyl diamines for ATH in the Johnson Matthey patent
By the end of the reaction (22 hours) Ts(pOMe)DPEN led to 90% conversion, while TsDPEN
only led to 70% conversion. The ee for both reactions was reported at 98%. In terms of practical
synthesis involving Ts(pOMe)DPEN, this ligand has been used in asymmetric transfer
hydrogenation of oxcarbazepine to eslicarbazepine, followed by acetylation to give
espicarbazepine acetate.30
7
1.1.3 Synthetic Applications of Resonance Assisted Hydrogen Bonds
Hydrogen bonds are probably the most thoroughly studied non-covalent interaction in all of
chemical space. Hydrogen bonds (H-bonds) arise from the significant dipole formed through the
bonding of hydrogen to highly electronegative atoms such as oxygen, nitrogen and fluorine. This
polarization leads to a charge differential along the bond that can be stabilized through non-
covalent interactions of the hydrogen with corresponding H-bond acceptor partners.31
Although the general framework for hydrogen bonding is well understood, there is considerable
variation among different types of hydrogen bonds. The geometric and thermodynamic
parameters of hydrogen bonds can vary depending on the precise nature of the interaction, and
many classes of H-bonds are known. The properties of these different H-bonds are often unique,
and pave the way for interesting developments in chemistry.
In seminal reports by Gilli and co-workers, hydrogen bonds were categorized into a number of
classes based on their chemical and structural origins. Broadly speaking, H-bonds can fall into
either the strong, moderate or weak categories, with further subdivisions accompanying these
distinctions. One of the strong types of H-bonds is termed resonance assisted hydrogen bonds
(RAHB), or alternatively, π-cooperative H-bonds.32 RAHBs arise when a hydrogen bond can be
stabilized through a resonance structure as with β-diketone enols (Figure 1.6). The result of the
RAHB is a particularly strong H-bond interaction with an O⋯O bond distance of between 2.39 –
2.55 Å and the energy of a RAHB is calculated at approximately 2.7 kcal/mol greater than weak
H-bonds.33
Figure 1.6: Resonance assisted hydrogen bonding in β-diketone enols leads to particularly
strong H-bonds.
8
Because of the energetic favourability of RAHB compared to typical (weak) H-bonds, allowing
these two types of H-bonds to equilibrate would lead to virtually complete formation of the
RAHB. A number of key syntheses have been enabled due to the energetic stabilization of
RAHB species.
Biologically, RAHBs are utilized in amino acid biosynthesis through transamination reactions
carried out by the cofactor, pyridoxal phosphate.34 In a similar vein, Shi et al. have developed a
synthetic method for producing primary amines that relies on the stabilization of RAHB.35,36
Additionally, Chin et al. reported a method, the diaza-Cope rearrangement (DCR), for making
chiral diamines starting from achiral substituted aldehydes, and a general chiral diamine. This
diamine, named the “Mother Diamine,” is capable of rearranging to form two RAHBs, and this
pushes the equilibrium almost exclusively towards the direction of the products (Figure 1.7).37,38
Figure 1.7: Synthetic applications of resonance assisted hydrogen bonding.
The diaza-Cope rearrangement method is particularly well suited for making a diverse set of
catalysts for Noyori’s asymmetric transfer hydrogenation reaction, which bears a monotosylated
diamine. The first step in the DCR involves formation of a diimine between the Mother Diamine
and two equivalents of aldehyde. The key mechanistic step in the diaza-Cope rearrangement is a
[3+3] sigmatropic rearrangement,39 which correspondingly generates two RAHBs along with a
single bond to connect the initial aldehydes. Furthermore, this rearrangement occurs
stereoselectively with overall inversion of absolute stereochemistry. Subsequent acid hydrolysis
of the diimine yields the desired chiral diamine derivative, along with two equivalents of
9
salicylaldehyde (Figure 1.8). In this way, many different diamines may be synthesized using one
general and facile method.
NH2
NH2
OH
OH
2Ar
ON
N
OH
OH
Ar
Ar [3+3] N
N
OH
OH
Ar
Ar NH2Ar
NH2Ar
Hydrolysis
Figure 1.8: Mechanism and scheme for the diaza-Cope rearrangement.
1.2 Research Goals
The aim of this research is to investigate the effects of electronic substitutions on the catalytic
activity of Noyori’s asymmetric transfer hydrogenation catalyst. A patent issued to Johnson
Matthey plc described the enhanced rate of hydrogenation for an electron-rich monotosylated
diamine. Our research challenges their observations and investigates other substituted diamines,
most easily accessed synthetically through the diaza-Cope rearrangement.
1.3 Results and Discussions
1.3.1 Synthesis of Monotosylated Daughter Diamine Derivatives as Catalyst Precursors
Four distinct para-substituted monotosylated diphenylethylenediamines were synthesized and
tested as ligands in ruthenium-catalyzed asymmetric transfer hydrogenation. Both electron
donating and electron withdrawing derivatives were explored. The following section describes
the synthesis of these ligands starting from Mother Diamine and the corresponding aldehyde.
The diaza-Cope rearrangement provides a general synthetic route for obtaining the desired
daughter diamines, as shown in the scheme above (Figure 1.8). Starting with (R,R)-hpen
(“Mother Diamine”), a series of aldehyde substrates were reacted to form the rearranged RAHB-
stabilized diimine in excellent yield (Table 1.1). The absolute stereochemistry of the product is
reversed during the DCR.
10
NH2
NH2
OH
OH
(R,R)-hpen
2.2 eq
EtOH60oC, 1 hr
R
O
N
N
OH
OH R
R
R %yield
OMe >99%
NMe2 >99%
F 81.9%
Table 1.1: Synthesis of substituted diimines.
The presence of a highly downfield peak (~13 ppm) representing the phenolic acidic proton
confirmed the identity of the rearranged diamine. Such downfield shifts are characteristic of
RAHBs, and will only be apparent following successful rearrangement.
Following the DCR, the diimine was hydrolyzed overnight in acidic organic solvent, to produce
a white or yellow precipitate of the daughter diamine salt that could be recovered by vacuum
filtration (Table 1.2).
N
N
OH
OH R
R
conc. HCl
Solvent20 min at 50oC
rt ON
NH3
NH3
R
R
Cl
Cl
OH O
11
R Solvent/HCl (%v/v) %yield
OMe THF/3% HCl 76.5%
NMe2 EtOH/5% HCl 75.6%
F THF/3% HCl 78.9%
Table 1.2: Synthesis of substituted diamine hydrochloride salts.
The diamine salt was then tosylated using p-toluenesulfonic acid. At least one additional
equivalent of base was required to neutralize the generated HCl. Two distinct but similar
methods were employed for the tosylation. Broadly, either the neutral form of the diamine was
first isolated and subsequently tosylated (Method A), or alternatively, the diamine salt was
deprotonated and tosylated in a single-pot reaction (Method B). The yield and method used for
the various tosylation reactions appears in Table 1.3. The products were used directly in the
hydrogenation with the active catalyst formed in situ, as will be described.
NH3
NH3
R
R
Cl
Cl
SO
OCl
Base
CH2Cl2 or CHCl30oC 2 hr
rt ONNH
NH2
R
R
SO
O
R %yield Method
H 41.3% Method A
OMe 48.8% Method A
NMe2 34.1% Method A
F 53.0% Method B
12
Table 1.3: Synthesis of TsDPEN and other substituted monotosyl diamines.
1.3.2 Technique for Monitoring Hydrogenation Kinetics
Before testing the monotosylated daughter diamines directly, it was necessary to develop an
experimental protocol by which to monitor the reaction kinetics. Noyori’s asymmetric transfer
hydrogenation has been realized in a number of different solvent systems using various reducing
agents. Furthermore, some of these reactions are performed in heterogenous mixtures involving
two-phase aqueous/organic suspensions. Since we were interested in detecting the influence of
electronic substituents on hydrogenation activity, it was important that the reaction be carried out
homogeneously. Otherwise, it would be impossible to assign any differences in catalytic activity
independently to electronic effects as opposed to other factors such as solubility.
Working off of a similar protocol to that of Kacer,40 we designed a method by which to measure
the hydrogenation kinetics. The reaction was carried out in a formic acid/triethylamine azeotrope
with a small amount of acetonitrile-d3 added to allow for 1H-NMR analysis. In this system,
formic acid functions as hydride donor with decarboxylation of carbon dioxide. Conditions were
chosen such that the molar ratio of formic acid to triethylamine was 6:7. Most reaction
conditions call for a 5:2 formic acid:triethylamine molar ratio,41 but there is precedent for
altering the azeotropic concentrations.42 For our purposes, a slightly basic solution was desired as
some of the diamine derivatives contained basic moieties that could otherwise become
protonated. The substrate to catalyst ratio (S/C) ranged from 100 to 500 and was optimized for
each reaction. The reaction was heated to 40°C and monitored by NMR.
Preliminary experiments were conducted to ensure that the experimental protocol was robust.
Using (R,R)-DPEN as diamine catalyst precursor and acetophenone as substrate, a series of
reactions were conducted to determine the degree of reproducibility. For the reproducibility tests
and catalyst loading optimizations, the reaction was monitored by recording the 1H-NMR spectra
at various time points. It was found that the results were quite reproducible under these
conditions.
Once the optimized reaction conditions were determined for the respective hydrogenations, the
time points were shortened and aliquots were transferred to NMR solvent to be analyzed. A
quenched flow technique was used with formic acid added to the NMR solvent. The acidic
13
environment deactivated the catalyst by shifting the equilibrium in favour of the protonated
ruthenium catalyst, preventing further hydrogenation.43 The relative integration of the methyl
singlet of the starting material and the methyl doublet of the product detected by 1H-NMR was
used to measure the yield of the reaction at each time point.
1.3.3 Electronic Effect of Monotosylated Diamine Substituents on Catalytic Activity
Using the protocol described in Section 1.3.2, we next set out to analyze the activity of the para-
substituted diamines in asymmetric transfer hydrogenation. The following charts show the
relative catalytic activities for a series of substituted diamines (Figure 1.9). Assuming first-order
rate kinetics, the units for the y-axis are –ln[acetophenone], where [acetophenone] represents the
percent of reactant at a given time point. The rate constant derived from the line of best fit of all
eleven time points is shown in Table 1.4.
Ph CH3
O[(cymene)RuCl2]2
Ligand
Ph CH3
OH
*40oC
14
Figure 1.9: Relative catalytic activity for a series of substituted monotosylated diamine ligands:
a) TsDPEN; b) Ts(pOMe)DPEN; c) Ts(pNMe2)DPEN; and d) Ts(pF)DPEN.
Ligand Rate constant (min-‐1) TOF (s-‐1) Relative Rate
(R,R)-‐TsDPEN 1.71*10-‐3 0.0057 1
(S,S)-‐Ts(pOMe)DPEN 1.63*10-‐3 0.0054 0.95
(S,S)-‐Ts(pNMe2)DPEN 1.59*10-‐3 0.0053 0.93
(S,S)-‐Ts(pF)DPEN 1.67*10-‐3 0.0056 0.98
Table 1.4: Rate of hydrogenation of acetophenone and TOF using variously substituted
monotosylated diamines as ligands. S/C = 200.
For the different catalysts, the rate of hydrogenation is remarkably similar. From our results,
there is no detectable electronic influence on the hydrogenation kinetics. Additionally, there is
excellent linear fit, suggesting that the pseudo first-order kinetics model is appropriate, even as
the reaction progresses. Any small deviation in observed catalytic activity is likely the result of
systematic uncertainties, such as ligand impurities and minute temperature fluctuations
(duplicates were performed so as to minimize random error). Furthermore, it is possible that for
Ts(pNMe2)DPEN, a fraction of the ligand will be protonated despite the basic environment, and
this could have greater influence on the outer-sphere catalyst-substrate interaction due to the
presence of counter-anions. Therefore, within the experimental error of this system, we conclude
15
that the electronic effect of DPEN substituents is negligible for the rate of asymmetric transfer
hydrogenation.
These findings are surprising in light of the patent issued to Johnson Matthey; in their patent,
they report a significantly higher rate of reaction for Ts(pOMe)DPEN relative to the TsDPEN
control. Intuitively, however, these results can be justified by remarking that the aromatic ring π-
system is not conjugated with the amine N-ligand electron donors. Since our reactions were
performed using acetophenone as substrate instead of α-tetralone, we cannot preclude a steric
influence of their ligand in the reaction. However, our results suggest that there is no general
electronic effect imparted by aromatic substituents on the monotosylated DPEN ligand.
1.3.4 Computational Studies
The activation energy for asymmetric transfer hydrogenation for ruthenium compounds with
different DPEN substituents was calculated at the level of DFT B3LYP/6-31G*. For ease of
calculation, simplified model systems were investigated. First, an oxygen atom was substituted
for the N-tosyl monotosylation site as shown in Figure 1.10. This compound has also been
shown to be active experimentally,44 and there is general agreement that oxygen is an acceptable
substitute for N-tosyl.45 Second, benzene was substituted for p-cymene as the η6-ligand, a change
that has also been previously documented.46 Third, instead of modeling acetophenone as the
substrate, as was performed experimentally, the much simpler formaldehyde was used. Although
this choice precludes the investigation of stereoselectivity, we are only interested in the effect of
diamine substituents on overall rate, and not selectivity. Fourth, instead of HCOOH�Et3N as the
H2 source with corresponding release of CO2, methanol was used which produced formaldehyde
as byproduct. Similar to the previous substitutions, there is experimental precedent to validate
this approximation. Isopropanol has been used widely in transfer hydrogenation with the Noyori
catalyst, and was actually the first reported system that was used.5 It is true that dehydrogenation
of methanol will be considerably more unfavourable, but since we are more interested in
differences imparted by the variously substituted ligands, rather than absolute activation
energies, this too is a valid approximation. Additionally, using methanol as H2 source has the
added advantage that the transition state for both hydrogen transfer steps are identical, further
reducing computational cost. The complete scheme is shown in Figure 1.10 below.
16
RuONH
XCH3OH
RuO
NH
X
X
CH2O
H
H
RuONH2
X
XCH2=O
H RuO
NH
X
X
CH2O
H
H
RuONH
X
XCH3OH
X
[A] [A-B]TS [B] [B-A']TS [A']
Figure 1.10: Model structures used for computational analysis of hydrogenation reaction
pathway for variously substituted diamine analogs.
Table 1.5 shows the relative energies for the different species. The energy of free methanol and
free formaldehyde is incorporated into the energy value for [A] and [B], respectively. These data
are displayed graphically in Figure 1.w. Only the energies for [A], [B] and [A-B]TS are shown for
ease of visual interpretation; since the energies for [B-A’]TS is identical to [A-B]TS and [A’] is
identical to [A], the graph would simply be symmetrical about energy [B].
X= [A]
(kcal/mol)
[A-‐B]TS
(kcal/mol)
[B]
(kcal/mol)
[B-‐A’]TS
(kcal/mol)
[A’]
(kcal/mol)
F 0 5.87 5.98 5.87 0
H 0 6.17 5.69 6.17 0
OMe 0 6.01 5.53 6.01 0
NMe2 0 5.87 5.37 5.87 0
Table 1.5: Energies for the different species participating in asymmetric transfer hydrogenation.
For each substituent, [A] has been assigned an energy value of zero.
17
Figure 1.11: Energy values (kcal/mol) for hydrogenation starting material and transition state.
The activation energy differences are predicted to fall within a narrow 0.3 kcal/mol range.
Furthermore, there is no obvious electronic trend seen with these values. Using the TsDPEN
analog as ligand, the reaction is predicted to have the slowest rate. In other words, both electron-
donating and electron-withdrawing ligands are predicted to have marginally accelerated rates.
Furthermore, there is no obvious steric trend. As the least sterically hindering ligand, the
TsDPEN analog would be expected to be an outlier with the Ts(pF)DPEN ligands closely
following. However, based on calculations, TsDPEN is predicted to be the slowest, while Ts(pF)
DPEN is predicted to be nearly identical with Ts(pNMe2)DPEN as the fastest, with
Ts(pOMe)DPEN in between. The most likely analysis is that, as in the experimental results, any
predicted differences in reaction rate are superficial, and that ligand substituents have little
impact on the rate of hydrogenation.
18
1.3.5 Contribution of Resonance Assisted Hydrogen Bonding Towards Rate of Hydrogenation
A corollary of our investigations into substituted monotosyl diamines led us to investigate the
effects of resonance-assisted hydrogen bonding on activation towards hydrogenation. An
experiment was carried out to assess the relative rates of hydrogenation between 2’-
hydroxyacetophenone and 4’-hyroxyacetophenone. The former is capable of RAHBs with the
hydroxyl group in the ortho position, while para-hydroxyacetophenone cannot. We found that
the rate of hydrogenation is significantly faster using 2’-hydroxyacetophenone as substrate.
The rate of ketone hydrogenation is intimately connected to the degree of activation of the C=O
bond. A greater partial positive charge on the carbonyl carbon leads to faster hydrogenation.
Generally, electron-donating groups such as hydroxyls decrease the rate of hydrogenation by
adding a negative charge to the carbonyl, while electron-withdrawing groups accelerate the rate.
Based on this logic, it would be expected that electron-donating hydroxyl substituents should be
expected to react more slowly than acetophenone, and indeed, the rate of 4’-
hydroxyacetophenone is about one half that of acetophenone. For 2’-hydroxyacetophenone,
however, the rate is nearly six times faster than for acetophenone, as shown in Figure 1.12.
19
Ar CH3
O
Ar CH3
OH
[(cymene)RuCl2]2(R,R)-TsDPEN
40oC*
Ar Rate constant (min-‐1) Relative Rate
1.71*10-‐3 1
HO
0.761*10-‐3 0.44
OH
10.2*10-‐3 5.96
Figure 1.12: Rate of hydrogenation using various substrates. S/C = 200.
20
The accelerated rate observed with 2’-hydroxyacetophenone compared to 4’-
hydroxyacetophenone derives from the resonance-assisted hydrogen bond. As shown in Figure
1.6, a significant resonance structure for 2’-hydroxyacetophenone places a positive charge on the
2’–OH group. Presumably this decreases the activation energy required to reach the transition
state for outer-sphere coordination of the substrate with the ruthenium catalyst, and subsequent
hydrogenation to the diol. Interestingly, the influence of the RAHB is more significant than the
electron-donating capacity of the hydroxyl substituent.
1.4 Conclusions and Future Work
Four monotosylated diphenylethylenediamine derivatives of various electronic substituents were
synthesized and applied towards the asymmetric transfer hydrogenation reaction developed by
Noyori. In spite of prior art describing the enhanced catalytic activity of Ts(pOMe)DPEN as
ligand relative to TsDPEN, we found that this activity was not general across different carbonyl
substrates. Computation likewise predicts only a very modest difference – if at all – in activation
energy associated with the different ligands.
Future work will be aimed at applying our technology platform for diamine synthesis towards
other applications, whether restricted to other hydrogenations, or expanded to unrelated systems.
We will continue to use the principles of molecular recognition to guide our pursuit of
identifying more robust diamines and introducing them into synthetic applications. Additionally,
although this was not the focus of the current project, the effect of DPEN substituents on the
stereoselectivity of the transfer hydrogenation reaction could also be investigated in the future.
1.5 Experimental
1.5.1 General Considerations
Commercial reagents were purchased from Sigma Aldrich, Fisher or Alfa Aesar and used
without further purification. Solvents were likewise purchased from commercial sources.
Columns were packed with SiliaFlash® F60 40-63µm silica (Quebec City, QC, CA). 1H, 13C
and 19F NMR spectra were recorded on either a Bruker Avance III 400, Varian Mercury 400 or
Varian VnmrS 400 spectrometer. NMR spectra were referenced to the residual solvent peak.
Data for 1H NMR are reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, d =
doublet, t = triplet, q = quartet, m = multiplet, br = broad), coupling constant (Hz), integration.
21
Data for 13C NMR are reported in terms of chemical shift (δ ppm). Data for 19F NMR are
reported as follows: chemical shift (δ ppm), multiplicity (d = doublet, t = triplet, q = quartet),
coupling constant (Hz).
For computational analysis, all calculations were performed using Spartan ’08 or Spartan ’10
from Wavefunction Inc. DFT computation at the B3LYP/6-31G* level was used to calculate the
optimized geometry and corresponding energies of starting material and transition states, where
indicated.
1.5.2 General Procedure for Daughter Diamine Synthesis
Diimine synthesis:
(1R,2R)-1,2-Bis(2-hydroxyphenyl)ethylenediamine (hpen) was added to ethanol (2.5 M) to give
a brown slurry. The corresponding aldehyde (2.2 eq) was added to solubilize the mixture. The
reaction was heated at 60°C for one hour and then allowed to cool to room temperature. The
resulting yellow precipitate was washed thoroughly with hexanes or ethanol and dried over
vacuum to yield the rearranged diimines.
Hydrolysis:
Method A: The diimine was dissolved in THF (0.1 M) and conc. HCl was added such that the
final concentration of the solution was 3% v/v HCl. The reaction was heated at 50°C for twenty
minutes, and then allowed to spin at room temperature overnight. The resulting white precipitate
was recovered by vacuum filtration.
Method B: The diimine was dissolved in ethanol (0.1 M) and conc. HCl was added such that the
final concentration of the solution was 5% v/v HCl. The reaction was heated at 50°C for twenty
minutes, and then allowed to spin at room temperature overnight. The resulting yellow
precipitate was recovered by vacuum filtration.
Deprotonation:
The diamine hydrochloride salt was dissolved in a minimum of deionized water. A small amount
of a concentrated aqueous NaOH solution was added such that the total moles of hydroxide was
0.5 equivalents greater than HCl. The mixture was extracted twice with methylene chloride,
22
dried over magnesium sulphate and evaporated under vacuum to yield the neutral diamines as
crystalline solids.
1.5.3 General Procedure for Monotosylation of Daughter Diamines
General Procedure A: The neutral diamine was dissolved in methylene chloride (100 mM)
along with triethylamine (100 mM) and was placed on ice. Under heavy spinning, a methylene
chloride solution of identical volume containing p-toluenesulfonyl chloride (100 mM) was added
dropwise over 20 minutes. The reaction was left to spin on ice for two hours and then allowed to
warm to room temperature and continued reacting overnight. Once finished, the contents were
washed with deionized water and then extracted twice with brine. The organic layer was dried
over magnesium sulphate and the solvent was removed under vacuum to produce a powder. The
crude solid was then subject to column chromatography. Optimized solvent systems were
determined using TLC, and typically ranged from 0–50% hexanes in ethyl acetate.
General Procedure B: The diamine hydrochloride salt was dissolved in deionized water
(250mM) and a saturated aqueous NaOH solution was added until the concentration of NaOH
reached 2 N. With mixing, chloroform was added at a ratio of 2.5:1 v/v relative to the water. The
reaction was placed on ice with heavy stirring. An equal volume of p-toluenesulfonyl chloride in
chloroform (100mM) was added dropwise over the course of 20 min such that the molar ratio of
diamine to sulfone was 1:1. The reaction was left to spin on ice for two hours and then allowed
to warm to room temperature and continued reacting overnight. Once finished, the contents were
washed with deionized water and then extracted twice with brine. The organic layer was dried
over magnesium sulphate and the solvent was removed under vacuum to produce a powder. The
crude solid was then subject to column chromatography. Optimized solvent systems were
determined using TLC, and typically ranged from 0–50% hexanes in ethyl acetate.
1.5.4 General Procedure for Asymmetric Transfer Hydrogenation Reactions
General Procedure For Testing Substituted Monotosyl Diamines:
In a 2D vial, 5.1mg of dichloro(p-cymene)ruthenium(II) dimer (0.0083 mmol) was added along
with 0.0166 mmol of monotosyl diamine. The precatalyst compounds were dissolved in 1mL of
acetonitrile-d3 (16.6mM catalyst) and heated at 40°C for at least one hour. In a separate vial, an
23
azeotropic mixture was formed by adding 113µL of formic acid and 490µL of triethylamine
(HCOOH:Et3N molar ratio of 6:7). 300µL of the precatalyst solution was added to the mixture (5
mM), followed by 117µL of acetophenone (1 mmol, 1 M). The solution was shaken gently,
transferred to a NMR vial and heated at 40°C. The cap of the NMR tube was punctured to allow
for evolution and escape of CO2.
The reaction was monitored either by recording NMR on the reaction vial itself, or by taking
aliquots. For the latter method, one drop of reaction solution was transferred to external NMR
solvent (CDCl3) at the following time points: 0, 20, 40, 60, 80, 100, 120, 150, 180, 210 and 240
minutes. The CDCl3 NMR solvent contained 1% v/v formic acid to quench the reaction. The
yield at each time point was determined by relative integration of the reactant acetophenone CH3
singlet and the product 1-phenyl-1-ethanol upfield shifted CH3 doublet. Since one peak of the
CH3 doublet overlapped with a spinning sideband of triethylamine, the integration for the other
peak was determined and multiplied by two throughout. Duplicate reactions were run for all
ligand (except for Ts(pNMe2)DPEN) and the plots were generated by averaging the results of the
two at each time point. A sample of the NMR spectrum with relevant peaks outlined appears
below. Peak A is the CH3 singlet for the acetophenone reactant; Peak B is the CH3 doublet for
the 1-phenyl-1-ethanol product.
General Procedure For Testing Substrates With Resonance Assisted Hydrogen Bonds:
In a 2D vial, 5.1mg of dichloro(p-cymene)ruthenium(II) dimer (0.0083 mmol) was added along
with 6.1 mg of (R,R)-TsDPEN (0.0166 mmol). The precatalyst compounds were dissolved in
1mL of acetonitrile-d3 (16.6mM catalyst) and heated at 40°C for at least one hour. In a separate
24
vial, an azeotropic mixture was formed by adding 113µL of formic acid and 490µL of
triethylamine (HCOOH:Et3N molar ratio of 6:7). 300µL of the precatalyst solution was added to
the mixture (5 mM), followed by 60µL of 2’-hydroxyacetophenone and 68mg of 4’-
hydroxyacetophenone (0.5 mmol, 0.5 M each). The solution was shaken gently to fully dissolve
the substrates, transferred to a NMR vial and heated at 40°C. The cap of the NMR tube was
punctured to allow for unrestricted evolution and escape of CO2.
The reaction was monitored either by recording NMR on the reaction vial itself, or by taking
aliquots. For the latter method, one drop of reaction solution was transferred to external NMR
solvent (DMSO-d6) at the following time points: 0, 20, 40, 60, 80, 100, 120, 150, 180, 210 and
240 minutes. The DMSO-d6 NMR solvent contained 1% v/v formic acid to quench the reaction.
For the conversion of 2’-hydroxyacetophenone, the yield at each time point was determined by
relative integration of the reactant CH3 singlet and the product 1-(2-hydroxyphenyl)ethan-1-one
upfield shifted CH3 doublet. The reduced product of 4’-hydroxyacetophenone, 4-(1-
hydroxyethyl)phenol, was insoluble in the NMR solvent. Therefore, to monitor this reaction, the
integration of the 4’-hydroxyacetophenone CH3 singlet was compared relative to the summed
integrations of the 2’-hydroxyacetophenone CH3 and the 1-(2-hydroxyphenyl)ethan-1-one CH3
doublet.
1.5.5 Energy Calculations For Catalysts, Reaction Intermediates and Transition States
Using Spartan ’08, structures were drawn as shown in the Tables below. Equilibrium Geometry
was calculated using DFT B3LYP/6-31G* for the staring material [A] and [B], including
methanol and formaldehyde. Transition State Geometry, also at the level of DFT B3LYP/6-
31G*, was used to calculate the energy of the four transition states. These were computed
following the determination of the Equilibrium Conformer at the level of Molecular Mechanics
MMFF (for starting material/intermediates) and Equilibrium Geometry at the level of Semi-
Emperical PM3 (for transition states) as starting point. For all calculations involving the catalyst,
a pseudopotential was used to model the ruthenium metal centre. The raw energy values for the
various computed starting material and intermediate structures appear below.
Table 1:
25
Entry Compound: Energy (Ha):
a [A]TsDPEN
-‐997.42768 RuONH
b [A]Ts(pOMe)DPEN
-‐1226.472442 RuONH
OMe
MeO
c [A]Ts(pNMe2)DPEN
-‐1265.359319
RuONH
NMe2
Me2N
d [A]Ts(pF)DPEN
-‐1195.895531
RuONH
F
F
e [B]TsDPEN
-‐998.632528 RuONH2
H
26
f [B]Ts(pOMe)DPEN
-‐1227.677544
RuONH2
H
OMe
MeO
g [B]Ts(pNMe2)DPEN
-‐1266.565676
RuONH2
H
NMe2
Me2N
h [B]Ts(pF)DPEN
-‐1197.099924 RuONH2
H
F
F
i Methanol -‐115.714395 CH3OH
j Formaldehyde -‐114.500474 CH2=O
The raw energy values for the transition state structures appear in the Table below.
Table 2:
Entry Compound: Energy (Ha):
a [A-‐B]TSTsDPEN
-‐1113.132246 Ru
ONH
CH2O
H
H
27
b [A-‐B]TSTs(pOMe)DPEN
-‐1342.177262
RuO
NH
CH2O
H
H
OMe
MeO
c [A-‐B]TSTs(pNMe2)DPEN
-‐1381.064362
RuO
NH
CH2O
H
H
NMe2
Me2N
d [A-‐B]TSTs(pF)DPEN
-‐1311.600573
RuO
NH
CH2O
H
H
F
F
1.5.6 Characterization Data
N
N
MeO
MeO HO
HO 2,2'-((1E,1'E)-(((1S,2S)-1,2-bis(4-methoxyphenyl)ethane-1,2-
diyl)bis(azanylylidene))bis(methanylylidene))diphenol: Synthesized using 6.6 mmol (1.61 g)
hpen. The product was obtained as a yellow powder (3.34 g, >99%). Characterization data: 1H
NMR (400 MHz, CDCl3) δ 13.34 (s, 2H), 8.30 (s, 2H), 7.32 – 7.21 (m, 2H), 7.14 (dd, J = 7.7,
1.7 Hz, 2H), 7.12 – 7.07 (m, 4H), 6.95 (dd, J = 8.4, 1.1 Hz, 2H), 6.83 – 6.73 (m, 6H), 4.66 (s,
2H), 3.75 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 165.92, 161.07, 159.01, 132.60, 131.83,
131.79, 129.05, 118.84, 118.78, 117.00, 113.90, 79.74, 55.34.
28
N
N
Me2N
Me2N HO
HO 2,2'-((1E,1'E)-(((1S,2S)-1,2-bis(4-(dimethylamino)phenyl)ethane-1,2-
diyl)bis(azanylylidene))bis(methanylylidene))diphenol: Synthesized using 4.0 mmol (983 mg)
hpen. The product was obtained as a yellow powder (2.49 g, >99%). Characterization data: 1H
NMR (400 MHz, CDCl3) δ 13.55 (s, 2H), 8.28 (s, 2H), 7.29 – 7.20 (m, 2H), 7.13 (dd, J = 7.7,
1.7 Hz, 2H), 7.10 – 7.04 (m, 4H), 6.93 (dd, J = 8.3, 1.0 Hz, 2H), 6.78 (td, J = 7.4, 1.1 Hz, 2H),
6.65 – 6.54 (m, 4H), 4.66 (s, 2H), 2.89 (s, 12H). 13C NMR (100 MHz, CDCl3) δ 165.38, 161.20,
149.97, 132.29, 131.70, 128.73, 127.85, 118.97, 118.62, 116.97, 112.54, 79.70, 40.69.
N
N
F
F HO
HO 2,2'-((1E,1'E)-(((1S,2S)-1,2-bis(4-fluorophenyl)ethane-1,2-
diyl)bis(azanylylidene))bis(methanylylidene))diphenol: Synthesized using 6.6 mmol (1.61 g)
hpen. The product was obtained as a yellow powder (2.467 g, 81.9%). Characterization data: 1H
NMR (400 MHz, DMSO-d6) δ 13.16 (s, 2H), 8.53 (s, 2H), 7.38 – 7.31 (m, 8H), 7.10 (ddt, J =
9.1, 6.1, 2.5 Hz, 4H), 6.89 – 6.83 (m, 4H), 5.10 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 166.54,
160.96, 135.12, 132.95, 131.99, 129.54, 119.06, 118.57, 117.06, 115.63, 79.67. 19F NMR (400
MHz, DMSO-d6) δ -114.87 (ddd, J = 14.8, 9.5, 5.6 Hz).
29
NH3H3N
OMeMeO
Cl Cl
(1S,2S)-1,2-bis(4-methoxyphenyl)ethane-1,2-diaminium chloride: Synthesized using 3.6
mmol (1.727 g) diimine. The product was obtained as a white solid (970 mg, 6.5%). 1H NMR
(400 MHz, DMSO-d6) δ 9.19 (s, 6H), 7.31 – 7.22 (m, 4H), 6.87 – 6.77 (m, 4H), 5.00 (s, 2H),
3.69 (s, 6H). 13C NMR (100 MHz, DMSO-d6) δ 159.42, 130.11, 125.19, 113.79, 56.26, 55.15.
NH3H3N
NHMe2Me2HN
Cl Cl
ClCl (1S,2S)-1,2-bis(4-(dimethylammonio)phenyl)ethane-1,2-diaminium chloride: Synthesized
using 3.7 mmol (1.86 g) diimine. The product was obtained as a yellow solid (1.23 g, 75.6%).
Characterization data: 1H NMR (400 MHz, D2O) δ 7.50 – 7.39 (m, 4H), 7.40 – 7.31 (m, 4H),
5.06 (s, 2H), 3.08 (d, J = 0.9 Hz, 12H). 13C NMR (100 MHz, D2O) δ 143.48 , 133.09 , 130.38 ,
121.49 , 56.23 , 46.05 .
H3N NH3
FF
ClCl
(1S,2S)-1,2-bis(4-fluorophenyl)ethane-1,2-diaminium chloride: Synthesized using 5.3 mmol
(2.4 g) diimine. The product was obtained as a white solid (1.33 g, 78.9%). Characterization
data: 1H NMR (400 MHz, DMSO-d6) δ 9.30 (s, 6H), 7.43 – 7.33 (m, 4H), 7.16 – 7.05 (m, 4H),
30
5.09 (s, 2H). 13C NMR (100 MHz, DMSO-d6) δ 160.91, 131.11, 129.50, 115.53, 55.99. 19F NMR
(400 MHz, DMSO-d6) δ -112.35 (ddd, J = 13.8, 8.6, 5.3 Hz).
HNH2N SO
O
(1R,2R)-N-p-Tosyl-1,2-diphenylethylenediamine: Synthesized with General Procedure A
using 1.9 mmol (411 mg) of neutral diamine. The product was obtained as a white powder (293
mg, 41.3%). Characterization data: 1H NMR (400 MHz, CDCl3) δ 7.32 (d, J = 8.3 Hz, 2H), 7.19
– 7.09 (m, 10H), 6.97 (d, J = 7.9 Hz, 2H), 4.40 (d, J = 5.6 Hz, 1H), 4.17 (d, J = 5.6 Hz, 1H), 2.32
(s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.59, 141.55, 139.41, 129.21, 128.49, 128.32, 127.51,
127.44, 127.10, 126.94, 126.91, 126.65, 63.36, 60.64, 21.51.
HNH2N SO
O
OMeMeO N-((1S,2S)-2-amino-1,2-bis(4-methoxyphenyl)ethyl)-4-methylbenzenesulfonamide:
Synthesized with General Procedure A using 0.8 mmol (215 mg) of neutral diamine. The product
was obtained as a white powder (164 mg, 48.8%). Characterization data: 1H NMR (400 MHz,
CDCl3) δ 7.37 – 7.29 (m, 2H), 7.08 – 6.95 (m, 6H), 6.72 – 6.63 (m, 4H), 4.31 (d, J = 5.6 Hz,
1H), 4.09 (d, J = 5.6 Hz, 1H), 3.75 (d, J = 7.1 Hz, 6H), 2.33 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 158.98, 158.93, 142.55, 137.36, 133.71, 131.52, 129.16, 128.24, 127.62, 127.05,
113.80, 113.75, 62.88, 60.02, 55.36, 55.28, 21.53.
31
HNH2N
NMe2Me2N
SO
O
N-((1S,2S)-2-amino-1,2-bis(4-(dimethylamino)phenyl)ethyl)-4-methylbenzenesulfonamide:
Synthesized with General Procedure A using 1.0 mmol (290 mg) of neutral diamine. The product
was obtained as an orange powder (120 mg, 34.1%). Characterization data: 1H NMR (400 MHz,
CD3CN) δ 7.37 – 7.31 (m, 2H), 7.10 – 7.03 (m, 2H), 6.97 – 6.90 (m, 2H), 6.88 – 6.82 (m, 2H),
6.54 – 6.48 (m, 2H), 6.48 – 6.42 (m, 2H), 4.13 (d, J = 7.2 Hz, 1H), 3.89 (d, J = 7.2 Hz, 1H), 2.83
(d, J = 9.1 Hz, 12H, 2.32 (s, 3H). 13C NMR (100 MHz, CD3CN) δ 149.79, 137.49, 129.23,
128.90, 127.83, 127.29, 127.16, 126.99, 112.34, 112.32, 62.70, 59.72, 40.64, 40.53, 21.41.
HNH2N SO
O
FF N-((1S,2S)-2-amino-1,2-bis(4-(fluoro)phenyl)ethyl)-4-methylbenzenesulfonamide:
Synthesized with General Procedure B using 2.3 mmol (743 mg) diamine hydrochloride. The
product was obtained as a beige powder (493 mg, 53.0%). Characterization data: 1H NMR (400
MHz, CDCl3) δ 7.36 – 7.30 (m, 2H), 7.12 – 7.07 (m, 2H), 7.07 – 7.00 (m, 4H), 6.91 – 6.77 (m,
4H), 4.31 (d, J = 5.4 Hz, 1H), 4.09 (d, J = 5.5 Hz, 1H), 2.35 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 129.32, 128.76, 128.68, 128.12, 128.04, 126.98, 115.56, 115.47, 115.34, 115.25,
62.78, 60.02, 21.52. 19F NMR (400 MHz, CDCl3) δ -114.52 (dq, J = 8.9, 4.6, 3.2 Hz), -114.90
(tt, J = 9.2, 5.2 Hz).
2
32
Chapter 2 The Origin of Stereoselectivity in the Jacobsen-Katsuki
Epoxidation
2.1 Introduction
2.1.1 Structural Considerations of the Jacobsen-Katsuki Epoxidation Catalyst With Respect to Stereoselectivity
Stereoselective catalysis employing transition metals bound to chiral ligands has been one of the
most revolutionary achievements in recent organic synthesis.47 A number of pioneers in the field
have been acknowledged with Nobel Prizes for developing such catalyst, all of which have
become household names amongst synthetic chemists. In 2001, the Nobel Prize was shared by
Sharpless, for his work in asymmetric epoxidation, along with Noyori and Knowles, for their
contributions to asymmetric hydrogenation. These systems are currently used widely in the fine
chemical industry to synthesize many important compounds such as pharmaceuticals,
agrochemicals, polymers and intermediates thereof.48
Following Sharpless’s breakthroughs, Jacobsen and Katsuki independently reported a new
catalyst for asymmetric epoxidation, which employed chiral, bulky manganese (III) salen
complexes. This catalyst was termed the Jacobsen catalyst (Figure 2.1). Kochi had shown
previously that achiral Mn(III) salen complexes could be used as catalysts for epoxidation.49 By
using a chiral diamine instead, epoxidation occurred stereoselectively, and Jacobsen’s catalyst
exhibited even greater selectivity and broader substrate scope than the previously identified
epoxidation catalysts.50
Figure 2.1: Jacobsen’s Mn(III) asymmetric epoxidation catalyst.
33
By exchanging the manganese metal centre for cobalt, and adjusting for appropriate reaction
conditions, the modified catalyst was effective in the stereoselective hydrolysis of unsymmetrical
epoxides. This reaction is proposed to proceed through hydrolytic kinetic resolution (HKR)
whereby only the matched epoxide undergoes hydrolysis while the unmatched epoxide does not
react.51
Notwithstanding the high selectivities carried out through these reactions, the origin of
stereoselectivity remains largely elusive. Considerable effort has gone into elucidating the
mechanism for both epoxidation and HKR, as well as the underlying origin of stereoselectivity.
Most explanations are either speculative or controversial, or incomplete with respect to
rationalizing the high degree of observed stereoselectivity.52 Nonetheless, a number of key
features have emerged that seem certain to be involved in the stereoselective communication
pathway. Furthermore, careful experiments have been conducted that help identify some
necessary elements for the selectivity.
The salen ligand binds the metal in a tetradentate square planar geometry with the two imine-
nitrogen atoms mutually cis, and the phenolic oxygen atoms cis as well. The remaining two
coordination sites (which when filled lead to an octahedral geometry) are variable depending on
the particular system, and the point along the reaction coordinate.
According to a number of early publications by the Jacobsen group, the stereoselectivity of the
epoxidation reaction is imparted by a restricted approach of the olefin substrate to the active
manganese oxide complex.50 Supposedly, the substrate approaches the manganese oxide bond in
a side-on manner (Figure 2.2). Because of steric reasons, the olefin must approach from only a
single side. Subsequent steric interaction between the catalyst and the olefin substituents leads to
the observed stereoselectivity.
34
N
N
H
HOMn
OO
Figure 2.2: Side-on approach of alkene to the manganese-oxo complex53
This depiction was the prevailing mechanistic explanation for Jacobsen’s asymmetric
epoxidation reaction until the new millennium, with some reports citing this mechanism as late
as 2008.54 Although a possible consequence of the chiral catalyst, the side-on approach alone
does not sufficiently explain the high level of stereoselectivity observed in the reaction, for
which the enantiomeric excess is often greater than 90%. Indeed, for any given reaction, it is
generally understood that the relative energies of the possible transition states, and not the
trajectory of approach, determines the stereoselectivity of a reaction.55 Thus a significant
difference in relative transition state energies would be a more likely explanation.
In light of this shortcoming, additional theories were proposed to explain the origin of
stereoselectivity in Jacobsen’s epoxidation reactions. Importantly, the crystal structure of a salen-
cobalt complex bound to aziridine56 showed that the salen ligand was tilted, or “canted” with
respect to the plane.57 One of the tBu-phenol groups points below the plane and the other tBu-
phenol group is directed above the plane. The salen step was not appreciated prior to this report,
but is now unanimously considered a crucial element in the origin of stereoselectivity for both
the cobalt- and manganese-salen catalysts.58 The direction of the respective phenyl group
orientations is dictated by the chiral diamine (Figure 2.3). This is particularly essential for
stereoselective epoxidation, as the salen step is locked with respect to the manganese oxide
(Mn=O).
35
MnO
N N
O MnO
N N
O
NH2
NH2
(R,R)-dach
H2NH2N
(S,S)-dach
(P) salen step (M) salen step
Figure 2.3: The salen step, engendered by the absolute stereochemistry of the diamine.
Realizing the relevance of the salen step in the stereoselectivity of the epoxidation, and the
importance of considering the transition state energies as opposed to the trajectories, the task
turned to harmonizing the newfound data with a novel catalytic mechanism. Most propose a
side-on manganese epoxide-bound transition state, with the alkene substituents oriented in the
direction of the bottom salen step. Such considerations appear in the following references.59,60
Interestingly, it has been shown that an achiral variant of Jacobsen’s catalyst can facilitate
asymmetric epoxidation in the presence of chiral nonracemic donor ligands. Katsuki showed that
chiral amines could be used with achiral Mn-salen catalysts to yield epoxides with good
enantioselectivity.61 More recently, List used his versatile chiral phosphate as donor ligand
through asymmetric counteranion-directed catalysis (ACDC),62 where both activity and
selectivity were marginally improved over the chiral version of Jacobsen’s catalyst in some
instances.63 The reasoning behind both of these observations is the same: for achiral Jacobsen
catalysts, the salen step is still present, but can be directed in either direction and may even be in
equilibrium between the two forms. The role of the chiral diamine is to lock the salen step in a
particular position, which then enables the stereoselectivity. Likewise, in the traditional Jacobsen
epoxidation and hydrolysis reactions, the chiral donor ligand serves to lock the salen step in
place. These findings emphasize the importance of the salen step feature in imparting
stereoselectivity.
36
2.1.2 The Mechanism of Manganese-salen Catalyzed Epoxidation
In addition to a controversial binding geometry, one of the factors complicating the elucidation
of the origin of stereoselectivity in the epoxidation reaction is a controversial mechanistic
pathway. Specifically, there is much debate surrounding the oxygen transfer step (or steps)
leading ultimately to olefin oxidation. In the epoxidation reaction, one C=C double bond is
broken, while two C–O single bonds are formed. These transformations could be accomplished
in a stepwise fashion, where either a radical,64 cationic,65 or metallaoxetane66 intermediate is
generated. Alternatively, the reaction could proceed through a concerted mechanism, where both
C–O bonds are formed simultaneously (Figure 2.4). There is convincing evidence that the
reaction is stepwise, at least in some instances, since trans-epoxides can be generated from Z-
alkenes.65 Nevertheless, there is strong support that a concerted mechanism may be involved as
well.52
Figure 2.4: Proposed mechanisms for Mn-catalyzed epoxidation of Z-alkenes. Pathway A and
Pathway B – both stepwise – proceed through a metallaoxetane and radical intermediate,
respectively. Pathway C is concerted and both carbon-oxygen bonds are formed during a high-
energy transition state.
37
In the proposed radical mechanism, the stereoselectivity-determining step occurs during the
formation of the second C–O bond. Theoretically, it would be expected that the concerted
mechanism would lead to a higher degree of stereoselectivity, although it is possible for a radical
method to produce epoxides with high ee as well. The actual mechanism may be dependent on
the substrate; for instance, conjugated alkenes are more likely to form a radical intermediate, as
these can be stabilized through resonance. It is also possible that both stepwise and concerted
mechanisms compete to varying degrees depending on the substrate and other reaction
conditions.67,68
Quite comprehensive studies by Linde et al. investigating substrates bearing pendant radical
clocks such as ((Z)-1-((1S,2S)-2-phenylcyclopropyl)prop-1-en-1-yl)benzene (Figure 2.5) led to
some interesting conclusions.69 The researchers noted that following the reaction, there was a
mixture of epoxides – none having undergone cis/trans isomerization – and ring-opened
products. Since the presence of any radical intermediate would have been expected to lead to
ring opening instead of epoxidation, this suggested that two mechanisms were at play, namely
both a concerted and stepwise reaction. In the concerted pathway, epoxides were generated,
while in the stepwise, radical pathway, ring opening was observed.
Figure 2.5: Radical clock ring opening of ((Z)-1-((1S,2S)-2-phenylcyclopropyl)prop-1-en-1-
yl)benzene.
However, careful studies by Adam et al. on the relative kinetics of ring opening versus cis/trans
isomerization found that the radical clock ring opening is slow (3.6*108 s-1) relative to the
isomerization step (~1011 s-1).70 Although no data was reported for the rate of formation of the
second C–O bond, this implies that there may be sufficient time to form a radical followed
immediately by the second C–O bond formation before ring opening occurs, but not enough time
38
for isomerization followed by C–O bond formation. Such a situation would lead to similar results
observed by Linde.
A recent publication by Corey and co-workers71 advocated for a stepwise method with a
carbocation intermediate, but went on to rationalize the stereochemical preference in light of its
formation. According to their reasoning, in the case of a conjugated terminal alkene such as
styrene, the first C–O bond would preferentially be formed between the Mn-oxo complex and the
CH2 carbon. Correspondingly, positive charge would accumulate on the other carbon atom, with
delocalization of the charge throughout the aromatic ring. Moreover, the carbocation is further
stabilized by the phenoxy oxygen of the salen ligand. Due to the placement of the t-Bu groups
resulting from the salen step, only one of the two salen oxygen atoms is tenable with respect to
carbocation stabilization because of steric effects (Figure 2.6). Presumably, this same logic could
be applied to epoxidations leading to two chiral centres, such as with β-methyl styrene.
O
Mn N
N
OO
tBu
tBu
tBu
tBu
O
Figure 2.6: Corey’s proposed pathway for Jacobson epoxidation of indene.71
39
2.1.3 The Nature of the Manganese-Oxide Bond and the Active Catalytic Species
The active manganese oxide species in the epoxidation is fundamental to the asymmetric oxygen
transfer step, and by extension, the nature of the manganese-oxide bond will influence the active
species. Most of the discussions on the stereoselectivity of the epoxidation reaction focused on a
Mn(V)=O active species. The Mn(V) oxidation state – leading to a d2 manganese compound –
was the earliest putative oxidant, dating back to the initial publications by Jacobsen7 and Kochi.49
Early studies by Kochi using UV spectroscopy identified the presence of a transient manganese-
oxo intermediate. However, this species decomposed at a slower rate than the observed
epoxidation, suggesting that it was not the active species, but rather a catalyst sink. This species
was assigned as the µ-oxo Mn(IV) dimer, presumably formed between a Mn(III) compound and
the active oxidizing agent Mn(V)=O.49 Later attempts at characterization using ESI-MS and MS-
MS led to confirming identification of both the Mn(V)=O and µ-oxo Mn(IV) dimer species.72
The hybridization of oxygen in the Mn(V)=O species itself is also not conclusive. Oxo ligands
are most traditionally formally considered as X2-type ligands, meaning that the oxygen is most
accurately depicted as sp2 hybridized. However, a number of metal-oxo bonds, including
manganese-oxo bonds, consider the oxo ligand as a LX2 ligand. There have been crystal
structures reported in the literature that support this model.73 In such instances, the oxygen can
be considered as sp hybridized with a corresponding Mn(V)≡O bond.74
In addition to these two species, a number of additional putative active species have been
identified and suggested. Some of these are otherwise similar compounds to the Mn(V)=O
species, except that the oxo ligand is instead either a hydroperoxy or alkylperoxy ligand. This
could be generated on route to the Mn(V)=O complex, assuming the Mn(III) → Mn(V)
oxidation occurs with intermediate formation of a Mn(IV)–O2R species. It is also suggested that
Mn(IV)–OH or Mn(IV)–OCl compounds may be involved as well. Another possibility for the
active catalytic species involves Mn(IV)=O compounds. This compound could arise from the
elimination of HCl by Mn(IV)–OH (chloride is typically either coordinated to the metal, or is a
counterion).70 Despite the numerous possibilities, the strongest evidence points towards a formal
oxidation state of five for the active manganese oxidant.71
40
For computational analysis, the nature of the manganese-oxo bond has implications not only with
respect to selecting the correct structure to analyze, but also in assigning the correct electron
configuration and corresponding multiplicity. Not surprisingly, a number of theoretical studies
have focused on this issue and reported on the suspected most stable ground state electronic
configuration. Specifically, using DFT B3LYP, Houk75 concluded that the Mn(III) catalyst is a
quintet, while the putative Mn(V) active species is most likely to be a triplet. However, the
authors note that there is a huge influence on the relative spin-state stability of the Mn(V) oxo
complex and that even singlet multiplicities are attainable. Furthermore, it should be noted that
these calculation were performed using the Mn-salen model structure shown in Figure 2.7 below,
and the presence of the salen step that would be present in reality with the full ligand may in fact
change the spin-state significantly as the geometry around the metal center is altered from
planarity.
O
N N
OMn
X
O
Figure 2.7: Manganese-oxo compound used for the calculation performed by Houk et al.75
2.2 Research Goals
This chapter will present a novel interpretation for the origin of stereoselectivity seen with
Jacobson’s asymmetric epoxidation catalyst. Our research aims to harmonize experimental
observations described in the literature, along with our own observations, as well as
computational and theoretical considerations. Our proposed theory beautifully explains the
preferential formation of one epoxide diastereomer through the reaction. A more robust
understanding of the catalytic method – along with the origin of stereoselectivity – can aid in the
development of novel catalysts with enhanced activities and selectivities.
41
2.3 Results and Discussion
2.3.1 Challenges With the Prevailing Model
To depict the challenges with the prevailing model, a combination of computational and
experimental results was considered. In this section, the computational analysis will be presented
first, followed by the experimental.
As computational motivation, we endeavored to see whether the experimental stereoselectivity of
the reaction was reflected in the thermodynamics of the system. Using cis-β-methyl styrene 1 as
our model substrate, we began by calculating the relative energies of the two possible trans-
epoxides bound to Jacobsen’s catalyst, namely (2S,3R)-2 and (2R,3S)-2. Independent of the
precise mechanism for epoxidation (see Section 2.1.2), in a side-on approach of the alkene to the
metal, the hybridization of the partially bound epoxide would most resemble sp3. Therefore, as
an approximation, it is possible to consider the bent epoxide-bound structure as analogous to the
transition state.
Based on literature experimental observations,50 when using the SS-enantiomer of Jacobsen’s
catalyst in a two-phase aqueous/CH2Cl2 system with NaOCl as terminal oxidant, compound 1
undergoes epoxidation to form (2S,3R)-2 in 92% ee (Figure 2.8). Intuitively then, it would seem
logical for (2S,3R)-2 to bind more favorably to the SS catalyst than (2R,3S)-2, especially in light
of the prevailing rationalization for the origin of stereoselectivity. Specifically, the theory posited
by Jacobsen and others suggests that the olefin interacts with the catalyst in a side-on manner. By
extension, this implies that the catalyst can only accommodate one bound conformation of the
olefin, and that this ‘expected’ epoxide must bind to the catalyst with greater stability than its
enantiomer.
42
SS-dach-LMn-(2S,3R)-2
0 kcal/mol
MM-Global Minimum
SS-dach-LMn-(2R,3S)-2
-1.32 kcal/mol
MM-Global Minimum
Figure 2.8: Experimental observations and computed relative energies of epoxide enantiomers
bound to the SS-Jacobsen catalyst. The ‘expected’ bound epoxide SS-dach-LMn-(2S,3R)-2 has
been assigned an energy value of 0 kcal/mol.
Surprisingly, solving for the global energy minimum of the two structures, the opposite,
‘unexpected’ epoxide enantiomer is predicted. Using molecular mechanics (MM), the
unexpected epoxide (i.e. (2S,3R)-2) is predicted to be 1.32 kcal/mol more stable than the
predicted enantiomer. In all of the computed structures, the oxygen of the epoxide is bound side-
on with respect to the catalyst, consistent with an sp3 orbital hybridization.
One other consideration of note regarding the olefin trajectory theory for stereoselectivity is the
absolute epoxide stereochemistry observed when using DPEN compared to dach as chiral
diamine. According to the trajectory theory, for (S,S)-5 (catalyst with dach), the olefin
approaches the metal-oxo bond in a side-on manner, as depicted in Figure 2.9. Since the diamine
is unsymmetrical, the side of the olefin with the smaller substituent preferentially travels above
the more sterically hindered side, while the larger substituent travels above the less sterically
hindered side.
43
O
tBu
Me
N
Ph
N
Ph
O
tBu
MeO
O
tBu
tBu
N N
O
tBu
tBuO
a(favoured) b
c
d
b
c
d (favoured)
a
(S,S)-5 (R,R)-6
HMePh
H
H HHPh
Me H
Figure 2.9: Aerial view of alkene approach to manganese-oxo complex as part of the proposed
pathway invoked by Jacobsen to explain the observed sense of stereoselectivity. The bold O
represents the manganese-oxo oxygen.
Under the framework of the trajectory theory, (S,S)-5 could be considered comparable to (R,R)-6
(catalyst with DPEN).50 That is to say, in both cases, the steric contribution from the diimine
bridge is oriented downwards on the left side of the catalyst (as drawn), while the steric
contribution from the right side is oriented upwards, both with respect to the oxo bond. However,
over the course of the epoxidation, (S,S)-5 gives the opposite absolute stereochemistry to (R,R)-
6, albeit with very similar ee. As a justification for this observation, it was proposed that the
olefin can approach the metal-oxo bond from the side of the diimine bridge when dach is the
chiral diamine (approach d), but cannot approach from the same trajectory when the DPEN
scaffold is used, due to the greater steric influence of the two phenyl rings. Instead, the olefin
approaches from the side of the salen-phenol ligand, but specifically from the side where the
DPEN phenyl ring is oriented downwards (approach a). Furthermore, the larger phenyl group is
preferentially oriented away from the bulky tert-butyl group, which leads to the observed sense
of stereoselectivity.
Although not impossible, this explanation necessitates two distinct mechanistic pathways for
similar catalysts that coincidentally lead to very similar stereoselectivities. A more elegant
explanation might be that both versions of the catalyst operate in a similar manner. Specifically,
this argument is possible if the trajectory is not the dominating factor, and rather the significant
interaction arises from the differences in energy upon olefin binding to the catalyst at the
transition state. Assuming the trajectory is not the key feature for imparting stereoselectivity, it is
44
less compelling to equate (S,S)-5 with (R,R)-6. Indeed, the structural geometry of the two
catalysts (i.e. (S,S)-5 and (S,S)-6) is strikingly similar in the vicinity of the metal-oxo bond, as
predicted by computational modeling.
The experimental motivation for investigating the merits of the side-on, trajectory approach is
based on studies using aziridine. Aziridine, instead of epoxide, has often been used as a transition
state analog for epoxidation.76 Aziridines can bind to the Jacobsen catalyst in solution more
strongly than epoxides, which provides a means by which to monitor the interaction empirically
by experiment. NMR analysis was performed to determine the equilibrium concentrations of
chiral cis-aziridines between bound states to each respective Jacobsen catalyst enantiomer. Using
(2R,3S)-2-phenyl-3-methylaziridine 4 (1.5mM) with equal amounts of (R,R)-3 and (S,S)-3
(15mM each), the aziridine bound preferentially to (S,S)-3 in a ratio of 3:1 (Figure 2.10). In
nearly perfect agreement with the computational analysis above, this corresponds to 0.65
kcal/mol lower energy for the ‘unexpected’ enantiomer. Importantly, similar computational
calculations using cobalt and chiral cis-2-phenyl-3-methylaziridine enantiomers instead of
manganese and the corresponding epoxide returned similar results with respect to relative
energies (Figure 2.11). Specifically, the difference in energy was predicted as 0.85 kcal/mol
with the ‘unexpected’ enantiomer again the lower energy binder.
O
N N
O
tBu tBu
tButBuCo
(S,S)-3
NH
Me Ph
(2R,3S)-4
O
N N
O
tBu tBu
tButBuCo
(R,R)-3
Cl
ClO
N N
O
tBu tBu
tButBuCo
Cl
O
N N
O
tBu tBu
tButBuCo
Cl
NH
PhMe
NH
PhMe
45
Figure 2.10: NMR competition reaction between (2R,3S)-‐2-‐phenyl-‐3-‐methylaziridine (4)
with: A) (R,R)-‐3; B) (S,S)-‐3; and C) equal mixture of (S,S)-‐3 and (R,R)-‐3. Results show a 3:1
preference for the mismatched aziridine-‐catalyst complex.
SS-‐dach-‐LCo-‐(2S,3R)-‐4
0 kcal/mol
MM-‐Global Minimum
SS-‐dach-‐LCo-‐(2R,3S)-‐4
-‐0.85 kcal/mol
MM-‐Global Minimum
Figure 2.11: Computed relative energies of aziridine enantiomers bound to the SS-‐Jacobsen
catalyst. The ‘expected’ bound aziridine SS-‐dach-‐LCo-‐(2S,3R)-‐4 has been assigned an energy
value of 0 kcal/mol.
2.3.2 Agreement of Computational Modeling with Experimental Observations
Whenever computational models are used, it is always prudent to question the accuracy of the
results with respect to describing the actual system. Fortunately, the computational findings for
the epoxide-bound Jacobsen catalyst can be supported by two key experimental observations,
46
both of which rely on the crystal structure of (2R,3S)-2-phenyl-3-methylaziridine 4 bound to both
(S,S)-3 and (R,R)-3, solved previously by our group (Figure 2.12).56
O
N N
O
tBu tBu
tButBuCo
3
NH
Me Ph
4
O
N N
O
tBu tBu
tButBuCo
NH
NH
Me Ph
MePh
(S,S)-3-[(2R,3S)-4]2
O
N N
O
tBu tBu
tButBuCo
NH
NH
Me Ph
MePh
(R,R)-3-[(2R,3S)-4]2
Figure 2.12: Crystal structures of (2R,3S)-2-phenyl-3-methylaziridine bound to both
enantiomers of the Jacobsen catalyst.
47
First, we will use a statistical motivation. In both the crystal structure and the computation, the
four atoms making up the salen core are coplanar. The resulting plane can be split up into
quadrants as shown in Figure 2.13a. The C–C single bond of the bound aziridine straddles two
of these quadrants to avoid unfavourable steric interactions between the hydrogen atoms and the
salen core. For each diastereomer (i.e. (S,S)-3-[(2R,3S)-4]2 and (R,R)-3-[(2R,3S)-4)]2), there are
four possible orientations that the aziridine can bind (Figure 2.13b-c). Based on the crystal
structures, it is known which orientation is the most stable. For both diastereomers, computation
predicts the correct orientation. For (2R,3S)-4 bound to (R,R)-3, both computation and the crystal
structure showed the aziridine straddling quadrant I//II as the most stable orientation. This is a
strong intuitive support that the computational model is describing the system correctly.
This agreement can be verified by comparing the relative energies of the complex with the
aziridine straddling each quadrant. Starting from the equilibrium conformer solved at the level of
Molecular Mechanics, the cobalt-nitrogen bond was iteratively rotated 90° such that all four
possible orientations were surveyed. At each position, the local equilibrium geometry was
calculated. For the conformer with aziridine straddling quadrant III/IV, a local minimum could
not be reached, and so the dihedral angle was constrained to prevent the geometry from
diverging too significantly such that the aziridine straddled quadrants IV/I.
O
N N
O
tBu tBu
tButBuCo
Cl
a
N N
OOI
II
III
IV
RR-LCo
48
N N
OONHPh
MeI
II
III
IV
b
N N
OONH
Ph
MeII
III
IV
I
N N
OOHN Ph
Me
II
III
IV
I
HN
PhMe
N N
OOII
III
IV
I
+4.09 kcal/mol +10.12kcal/mol +9.14 kcal/mol 0 kcal/mol
N N
OO
I
II
III
IVNHPh
Me
c
N N
OOI
II
III
IVNH
Ph
Me
HN Ph
MeN N
OOI
II
III
IV
N N
OOI
II
III
IVHN
Ph
Me
0 kcal/mol +0.86 kcal/mol +7.83 kcal/mol +1.19 kcal/mol
Figure 2.13: a) (R,R)-‐3, with the corresponding cartoon Lewis representation used
throughout. b) Four possible orientations of (2R,3S)-‐2-‐phenyl-‐3-‐methylaziridine bound to
(S,S)-‐3. The lowest energy conformer has been assigned an energy value of 0 kcal/mol. c) Four
possible orientations of (2R,3S)-‐2-‐phenyl-‐3-‐methylaziridine bound to (R,R)-‐3. The lowest
energy conformer has been assigned an energy value of 0 kcal/mol.
As seen from the Figure, for the lowest energy conformer of (2R,3S)-4 bound to (S,S)-3, the
aziridine straddles quadrants IV/I. For the lowest energy conformer of (2R,3S)-4 bound to (R,R)-
3, the aziridine straddles quadrants I/II. The same bonding mode is observed in the crystal
structures (Figure 2.14, Figure 2.15). From a statistical standpoint, any of the four possible
quadrant overlaps are theoretically attainable. This is likewise true for the second bound
aziridine, leading to sixteen possible conformations for the bis-ligated catalyst. Taking into
consideration the second diastereomer, another sixteen conformers are possible. The fact that the
computational analysis predicts the same orientation as is apparent in the crystal structure – for
both diastereomers – is promising.
49
Figure 2.14: Side view (top) and aerial view (bottom) of (2R,3S)-‐4 bound to (S,S)-‐3. Crystal
(left) and computed (right) structures are compared.
50
Figure 2.15: Side view (top) and aerial view (bottom) of (2R,3S)-4 bound to (R,R)-3. Crystal
(left) and computed (right) structures are compared.
Perhaps more compellingly, alignment of the crystal structure with the computed structure shows
a high degree of similarity. For the (S,S)-dach structure, the alignment score is calculated as 0.97
using Spartan, which is measured on a scale of 0 to 1. This corresponds to a RMSD of 0.60 Å for
all non-hydrogen atoms, which confirms the excellent agreement quantitatively. For the (R,R)-
dach structure, the alignment score could not be calculated, but the RMSD was 0.42 Å, again in
excellent quantitative agreement. The overlapping structures for each diastereomer appear below
(Figure 2.16).
(S,S)-‐dach
Calculated RMSD: 0.60 Å
(R,R)-‐dach
Calculated RMSD: 0.42 Å
51
Figure 2.16: Aligned structures of (S,S)-‐3 and (R,R)-‐3 bound to (2R,3S)-‐4 determined by
both X-‐ray crystallography (gray) and molecular modeling computation (red). Hydrogen
atoms have been excluded for clarity.
2.3.3 Advantages Offered By Considering A Planar Transition State
With an appreciation of the limitations in the side-on transition state theory, and a working
computational model in hand, we ventured to address other possible origins of stereoselectivity
in the Jacobsen-Katsuki epoxidation. We found that by considering a novel binding mode,
computation gave the proper prediction for stereoselectivity. Specifically, if the epoxide was
considered to be planar rather than bent (as in the side-on mechanism), the proper
stereoselectivities were predicted computationally. Again using 2-phenyl-3-methylaziridine as
substrate, we calculated the global equilibrium conformer using molecular mechanics for both
diastereomers (Figure 2.17).
SS-‐dach-‐LCo-‐(2S,3R)-‐4
0 kcal/mol
MM-‐Global Minimum
SS-‐dach-‐LCo-‐(2S,3R)-‐4
+1.54 kcal/mol
MM-‐Global Minimum
Figure 2.17: Experimental observations and computed relative energies of epoxide
enantiomers bound to the SS-‐Jacobsen catalyst. The ‘expected’ bound deprotonated
aziridine SS-‐dach-‐LCo-‐(2S,3R)-‐4 has been assigned an energy value of 0 kcal/mol.
It is important to note how the cyclic aziridine ring lies in the same plane as the metal and
chloride axial ligand. We refer to this structure as the planar transition state analog. In order to
make the aziridine planar, the N–H hydrogen of the aziridine nitrogen was removed. This was
52
meant to approximate a sp2-oxygen at the transition state; at the level of molecular mechanics,
oxygen was restricted to sp3 geometry (side-on), but higher level calculations do predict a planar
oxygen depending on the number of bonds at the transition state. Further expansion of these
calculations, as well as the rationale behind using deprotonated aziridine, will be discussed in
Section 2.3.4.
Using the planar transition state analog, the correct stereoselectivity is predicted with (2S,3R)-4
binding to (S,S)-3 more strongly than its (2R,3S)-4 enantiomer by 1.54 kcal/mol. In stark contrast
to the side-on transition state analog, not only does the planar model predict the correct
stereoselectivity, but it also agrees quite closely with experimental ee observations. The reactions
reported by Jacobsen were performed at 4°C. At this temperature, 1.54 kcal/mol corresponds to
an equilibrium constant of 16.5 in favour of the expected aziridine, which corresponds to a
predicted ee of 88.6%. The literature reported ee is 92%.
Another advantage of the planar epoxidation mechanism is that it explains the other experimental
results observed by Jacobsen and his group. As mentioned, a distinct mechanism was invoked to
explain the stereoselectivity preference of the Jacobsen catalyst bearing DPEN as chiral diamine.
As with the dach catalyst 3, the planar transition state analog predicts the correct
stereoselectivity, while the side-on transition state incorrectly predicts the unobserved
enantiomer. Similarly, computation correctly predicts the erosion of stereoselectivity observed
with the dimethyl-dach chiral diamine version when modeling the planar transition state analog.
Although the diminished stereoselectivity is not predicted to be as dramatic as experimentally
observed, the trend is identical such that (S,S)-dach produces the highest selectivity, followed
closely by (S,S)-DPEN, and then by (S,S)-Me-dach. The tabulated comparisons appear in Table
2.1. For all computed calculations, global energy minimum structures were determined using the
Equilibrium Conformer search at the level of Molecular Mechanics.
53
Catalyst TSa
Experimental
Epoxide
Configuration
Literature ee,
%
Computed
ΔE
(kcal/mol)b
Predicted ee,
%c
(S,S)-‐dach Planar (2S,3R) 92 +1.54 88.6
(S,S)-‐DPEN Planar (2S,3R) 84 +1.51 87.9
(S,S)-‐Me-‐dach Planar (2S,3R) 55 +1.25 81.2
(S,S)-‐dach Bent (2S,3R) 92 -‐0.85 Opposite
(S,S)-‐DPEN Bent (2S,3R) 84 -‐0.89 Opposite
(S,S)-‐Me-‐dach Bent (2S,3R) 55 -‐2.14 Opposite
O
tBu
N N
O
tBu
tButBuMn
Cl
(S,S)-dach
O
tBu
N N
O
tBu
tButBuMn
Cl
(S,S)-Me-dach
O
tBu
N N
O
tBu
MeMeMn
Cl
(S,S)-DPEN
Ph Ph
Table 2.1: Comparison of literature experimental results with computational prediction
for a variety of catalysts. Both planar and bent transition states are considered. aDeprotonated sp2 aziridine used for planar transition state (TS), sp3 aziridine used for
bent transition state. bDifference in energy between bound (2R,3S)-‐4 (not observed) and
(2S,3R)-‐4 (observed). cSee Experimental section for predicted ee calculations.
With the excellent agreement between experimental observations and the planar mechanism
using β-methyl styrene, along with the shortcomings of the bent, side-on approach at explaining
stereoselectivity, we decided to screen for additional substrates. In Jacobsen’s 1991 paper, six
54
substrates were analyzed for application in asymmetric epoxidation using (S,S)-dach as catalyst.
As shown in Table 2.2, the planar model is greatly superior to the bent model for predicting the
sense of stereoselectivity and by extension, the more stable transition state analog diastereomer.
Substrate TSa
Experimental
Epoxide
Configuration
Literature
ee, %
Computed
ΔE
(kcal/mol)b
Predicted
ee, %c
Ph Me
Planar (2S,3R) 92 +1.54 88.6
Me p-ClC6H4
Planar (2S,3R) 92 +1.44 86.3
O
Planar (1aS,7bS) 98 +1.14 77.6
O
NC
Planar (1aS,7bS) 97 +1.43 86.2
O
O
Planar (1R,6R) 94 -‐0.04 Opposite
MeO2C Ph
Planar (2S,3S) 89 +3.59 99.7
Ph Me
Bent (2S,3R) 92 -‐0.85 Opposite
Me p-ClC6H4
Bent (2S,3R) 92 -‐1.67 Opposite
O
Bent (1aS,7bS) 98 -‐0.14 Opposite
55
O
NC
Bent (1aS,7bS) 97 -‐1.43 Opposite
O
O
Bent (1R,6R) 94 +6.56 >99.9
MeO2C Ph
Bent (2S,3S) 89 -‐3.47 Opposite
Table 2.2: Comparison of literature experimental results with computational prediction for
a variety of substrates. (S,S)-‐dach was used as catalyst throughout. Both planar and bent
transition states are considered. aDeprotonated sp2 aziridine used for planar transition
state (TS), sp3 aziridine used for bent transition state. bDifference in energy between bound
(2R,3S)-‐4 (not observed) and (2S,3R)-‐4 (observed). cSee Experimental section for predicted
ee calculations.
Undoubtedly, the planar transition state is superior at predicting the sense of stereoselectivity
compared to the prevailing bent model. Of the six substrates reported by Jacobsen, the sense of
stereoselectivity is predicted correctly for five of them using the planar TS model. Conversely,
the bent TS model predicts the incorrect sense of stereoselectivity for five of the six substrates. It
is also worth mentioning that the planar model obviates the need to consider the trajectory of the
incoming olefins, which could theoretically be quite different depending on the structure and the
resulting steric considerations.
For the one incorrectly predicted entry using the planar geometry, the substrate is very flexible
with many possible degrees of freedom. This complicates the global minimum calculation and
may be the source of the error. Furthermore, across the board, there is good agreement between
the predicted energy difference between the two enantiomeric bound aziridines, and the observed
ee.
56
2.3.4 The Hybridization of the Axial Oxygen Ligand
In order for the transition state to be planar, the oxygen must have sp or sp2 character at that time.
In this section, we will present computational analysis that supports this type of hybridization at
the transition state.
To start, it is important to identify which manganese-oxo compound is most stable, and whether
this is a likely compound to be involved in the epoxidation. With this goal in mind, we calculated
the energies of the different possible manganese compounds using DFT B3LYP/6-31G*
computation. Three potential electronic states are possible for octahedral manganese-oxo
compounds: singlet, triplet and quintet. These three multiplicities correlate roughly to triple,
double and single bond order, respectively, along the Mn–O bond.74
Multiplicity Bond Order Energy (kcal/mol) dMn–O (Å) Oxygen Partial Charge
Singlet Triple +13.558 1.558 -‐0.461
Triplet Double 0 1.757 -‐0.451
Quintet Single +2.380 1.773 -‐0.505
O
N N
O
tBu tBu
Mn
Cl
O
Table 2.3: Relative energies and other computed physical properties of potential (salen)Mn=O
species. Bond orders values are qualitative. The most stable, triplet species has been assigned an
energy value of 0 kcal/mol.
As can be seen in Table 2.3, the triplet is the most stable predicted state, nearly 2.5 kcal/mol
more stable than the quintet. The singlet is predicted to be over 10 kcal/mol less stable than both
the triplet and the quintet, and cannot be a significant player in the epoxidation reaction.
57
Additionally, the Mn–O bond lengths and the partial charge on the oxygen were determined. The
triplet species also has the least negative oxygen, which is important considering that the catalyst
is the electrophile. Parenthetically, these calculations validate those performed by Houk75 on the
simpler model systems (discussed in Section 2.1.3). For ease of calculation, the tert-butyl groups
in the para-position were not included in this analysis.
Aside from the calculated partial charges on the oxygen atom, the molecular orbitals generated
for the various structures also shed insight on the active manganese-oxo species. In the
asymmetric epoxidation reaction, the olefin double bond acts as the nucleophile, while the
manganese-oxo complex acts as the electrophile. Figure 2.18 shows the HOMO orbital for a
model olefin, cis-2-butene, along with the LUMO orbitals for the three manganese-oxo species.
Again, the orbitals of the triplet species seem to have the greatest complementary overlap with
the incoming olefin.
Figure 2.18: HOMO and LUMO orbitals of cis-2-butene and the Jacobsen manganese-oxo
catalyst, respectively. The LUMO for all three potential manganese multiplicity states are shown.
Seeing as the manganese-oxo triplet is the most stable species, and that the electronic situation
favours bonding of the olefin to this complex, our further analysis will focus on the triplet as the
active species. Importantly, based on the double bond nature of the Mn-oxo species, and the
HOMO-LUMO representations, at least early on in the reaction trajectory, the olefin should be
bound in a planar sp2 configuration.
58
Further calculation has identified the epoxidation as highly exothermic. The transfer of oxygen
from manganese to the alkene to form the epoxide is predicted to be downhill by at least 23
kcal/mol. During the transfer of oxygen from the manganese-oxo triplet to cis-2-butene, the
manganese could either remain in the triplet state, or cross over to the more stable quintet state in
a concerted fashion.74 Table 2.4 shows the calculated energies of the products and reactants,
along with the energy associated with the oxygen transfer.
O
N
tBu
N
O
tBu
MnO
N
tBu
N
O
tBu
MnO
Cl Cl
MeMe MeMe
O
L-MnCl=O L-MnCl dimethyloxiranecis-2-butene
EL-‐MnCl=O Ecis-‐2-‐butene EL-‐MnCl Edimethyloxirane ΔEreaction
-‐1904519.572
(triplet)
-‐98660.026 -‐1857352.572
(triplet)
-‐145851.090 -‐23.834
-‐1904519.572
(triplet)
-‐98660.026 -‐1857375.963
(quintet)
-‐145851.090 -‐47.456
Table 2.4: Calculated energies (in kcal/mol) using DFT B3LYP/6-‐31G* of products and
reactants involved in oxygen transfer epoxidation. ΔE of reaction is also shown for two
potential pathways.
Due to the high exothermicity, according to the Hammond postulate, this would suggest a
relatively early transition state. In other words, the transition state should resemble the reactants.
Seeing as the initial manganese-oxo oxygen is sp2 hybridized, it follows that in an early
transition state, the oxygen would also be approximately sp2-hybridized. This would result in a
planar transition state. Therefore, a planar transition state not only explains the observed
stereoselectivity, but is also predicted based on electronic considerations.
59
2.4 Conclusions and Future Work
Here we have provided an alternative asymmetric epoxidation mechanism to the commonly held
side-on approach of the alkene. Instead of focusing on a bent transition state for epoxide
formation, the investigation of a planar transition state with an approximately sp2-hybridized
manganese-oxo oxygen was considered. Protonated or deprotonated aziridines bound to the
Jacobsen cobalt complex were used to represent bent or planar transition state analogs,
respectively. The planar transition state analog was superior with respect to predicting the
experimentally observed sense of stereoselectivity compared to the bent model. For all three
catalyst systems, and for five out of six substrates tested by Jacobsen, the planar model correctly
predicted the energetically preferred absolute stereochemistry.
It is important to note that a major advantage of our technique lies in its computational
simplicity. For each diastereomer, the calculations used to predict the global energy minimum
conformer can be run in less than one minute each on a standard desktop computer, and at the
level of molecular mechanics. The DFT calculations described are simply meant to validate the
method and are not necessary to determine the sense of stereoselectivity. This allows a facile
method for routinely screening substrate-catalyst pairs to predict the expected product
stereochemistry. Moreover, if a desired product displays poor stereoselectivity, this method
could be used to rationally design novel related catalysts that could be used instead of the
traditional Jacobsen catalyst. If the planar transition state analog does play a significant role in
the origin of epoxide stereoselectivity as our analysis suggests, similar explorative computational
modeling could obviate the need for high-throughput catalytic screening, and streamline the
implementation of optimized epoxidation catalysts.
Lastly, our work is not restricted to manganese-salen catalyzed epoxidation. We believe that our
computational modeling approach can be applied to other catalyst systems, as well. We are
currently working on a mechanistic explanation for cobalt-salen catalyzed epoxide hydrolysis as
a similar, but slightly different system. Ongoing efforts will be aimed at investigating yet other
organometallo- and organo-catalytic systems in the future. Our hope is that through this work,
more efficient catalysts will be developed and applied to practically relevant syntheses.
60
2.5 Experimental
2.5.1 General Considerations
All calculations were performed using Spartan ’08 or Spartan ’10 from Wavefunction Inc. MM
computation at the level of MMFF was used to calculate the equilibrium geometry, and global
equilibrium conformer, where indicated. DFT computation at the B3LYP/6-31G* level was used
to calculate the optimized geometry and corresponding energies of manganese-oxo complexes,
as well as olefin and epoxide energies, where indicated. Crystal structure and computed structure
RMSD values were calculated using VMD, developed by the Theoretical and Computational
Biophysics Group at the University of Illinois at Urbana-Champaign.77
2.5.2 Energy Calculations On Bent Geometry Transition State Analogs
The epoxidation catalyst was constructed using hexavalent mangenese bound to tetradentate 6,6'-
((1E,1'E)-(((1S,2S)-cyclohexane-1,2-diyl)bis(azanylylidene))bis(methanylylidene))bis(2,4-di-
tert-butylphenolate), and mutually axial chloride and 2-phenyl-3-methyloxirane. Equilibrium
conformers for both the (2S,3R)- and (2R,3S)-enantiomers were calculated and the energies were
compared.
Table 1:
Entry Compound: Energy (kJ/mol):
a (2S,3R)-‐ 2-‐phenyl-‐3-‐methyloxirane 1031.1823
O
N N
O
tBu tBu
tButBuCo
Cl
O
Me Ph
b (2R,3S)-‐ 2-‐phenyl-‐3-‐methyloxirane 1025.6393
O
N N
O
tBu tBu
tButBuCo
Cl
O
Me Ph
The same calculation was also performed using cobalt as metal instead of manganese, and 2-
phenyl-3-methylaziridine instead of 2-phenyl-3-methyloxirane. The aziridine nitrogen was
drawn with tetrahedral geometry (including the Co–N bond) and is consequently modeled as sp3.
61
Table 2:
Entry Compound: Energy (kJ/mol):
a (2S,3R)-‐ 2-‐phenyl-‐3-‐
methylaziridine
687.7479
O
N N
O
tBu tBu
tButBuCo
Cl
NH
Me Ph
b (2R,3S)-‐ 2-‐phenyl-‐3-‐
methylaziridine
684.1726
O
N N
O
tBu tBu
tButBuCo
Cl
NH
Me Ph
The Table below shows the absolute energies for the various catalyst and substrate pairs
discussed throughout the chapter:
Table 3:
Entry Catalyst: Substrate: Energy (kJ/mol):
a (S,S)-‐DPEN (2S,3R)-‐ 2-‐phenyl-‐3-‐
methylaziridine 756.2727
O
N N
O
tBu tBu
MeMeCo
PhPh
Cl
NH
Ph Me
b (S,S)-‐DPEN (2R,3S)-‐ 2-‐phenyl-‐3-‐
methylaziridine 752.5520
O
N N
O
tBu tBu
MeMeCo
PhPh
Cl
NH
Me Ph
c (S,S)-‐Me-‐dach (2S,3R)-‐ 2-‐phenyl-‐3-‐
methylaziridine 824.8707
O
N N
O
tBu tBu
tButBuCo
Cl
NH
MePh
62
d (S,S)-‐Me-‐dach (2R,3S)-‐ 2-‐phenyl-‐3-‐
methylaziridine 815.9006
O
N N
O
tBu tBu
tButBuCo
Cl
NH
PhMe
e (S,S)-‐dach (2S,3R)-‐2-‐(4-‐chlorophenyl)-‐3-‐
methylaziridine 698.3842
O
N N
O
tBu tBu
tButBuCo
Cl
NH
Me
Cl
f (S,S)-‐dach (2R,3S)-‐2-‐(4-‐chlorophenyl)-‐3-‐
methylaziridine 691.3819
O
N N
O
tBu tBu
tButBuCo
Cl
NH
Me
Cl
g (S,S)-‐dach (1aS,7bS)-‐2,2-‐dimethyl-‐1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine
791.5741
O
N N
O
tBu tBu
tButBuCo
Cl
NH
O
h (S,S)-‐dach (1aR,7bR)-‐2,2-‐dimethyl-‐
1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine
790.9943
O
N N
O
tBu tBu
tButBuCo
Cl
NH
O
i (S,S)-‐dach (1aS,7bS)-‐2,2-‐dimethyl-‐1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine-‐6-‐carbonitrile
856.2541
O
N N
O
tBu tBu
tButBuCo
Cl
NH
ONC
63
j (S,S)-‐dach (1aR,7bR)-‐2,2-‐dimethyl-‐
1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine-‐6-‐carbonitrile
850.2630
O
N N
O
tBu tBu
tButBuCo
Cl
NH
O CN
k (S,S)-‐dach (1R,6R)-‐7-‐
azaspiro[bicyclo[4.1.0]heptane-‐
2,2'-‐[1,3]dioxolane]
707.3456
O
N N
O
tBu tBu
tButBuCo
Cl
NH
O
O
l (S,S)-‐dach (1S,6S)-‐7-‐
azaspiro[bicyclo[4.1.0]heptane-‐
2,2'-‐[1,3]dioxolane]
734.8075
O
N N
O
tBu tBu
tButBuCo
Cl
NHO
O
m (S,S)-‐dach methyl (2S,3S)-‐3-‐
phenylaziridine-‐2-‐carboxylate 765.0462
O
N N
O
tBu tBu
tButBuCo
Cl
NH
Ph CO2Me
n (S,S)-‐dach methyl (2R,3R)-‐3-‐
phenylaziridine-‐2-‐carboxylate 750.5353
O
N N
O
tBu tBu
tButBuCo
Cl
NH
MeO2C Ph
2.5.3 Energy Calculations for Different Quadrants
The (salen)CoCl catalyst bound to (2R,3S)-2-phenyl-3-methylaziridine was entered into Spartan.
Identical calculations were performed for both the (S,S)- and (R,R)-salen enantiomers, as follows.
The Equilibrium Conformer was determined using Molecular Mechanics MMFF calculations.
The quadrants were assigned arbitrarily as shown in the figure (Figure 2.13). Local minima for
the axial aziridine place the C–C bond between two quadrants; an upper limit of four local
minima are thus attainable following rotation of the Co–N(aziridine) bond. For each diastereomeric
pair, the Co–N(aziridine) bond was iteratively rotated 90° such that all four possible orientations
64
were surveyed. For each diastereomer, only three unconstrained local minima were attainable.
For (R,R)-Co, the C(az,phenyl)-N(aziridine)-Co-N(salen) dihedral angle was constrained at -43.48°, while
for (S,S)-Co, the C(az,phenyl)-N(aziridine)-Co-N(salen) dihedral angle was constrained at 51.72°. The
absolute energies for the conformers appear in the Table below.
Table 4:
N N
OONHPh
MeI
II
III
IV
b
N N
OONH
Ph
MeII
III
IV
I
N N
OOHN Ph
Me
II
III
IV
I
HN
PhMe
N N
OOII
III
IV
I
664.8259 kJ/mol 689.9567 kJ/mol 685.9285 kJ/mol 647.7059 kJ/mol
N N
OO
I
II
III
IVNHPh
Me
c
N N
OOI
II
III
IVNH
Ph
Me
HN Ph
MeN N
OOI
II
III
IV
N N
OOI
II
III
IVHN
Ph
Me
108.4031 kJ/mol 112.0156 kJ/mol 141.1657 kJ/mol 113.3730 kJ/mol
2.5.4 Energy Calculations on Planar Geometry Transition States
The deprotonated aziridine nitrogen was drawn with trigonal planar geometry (including the Co–
N bond) and is consequently modeled as sp2.
Table 5:
Entry Catalyst: Substrate: Energy (kJ/mol):
a (S,S)-‐dach (2S,3R)-‐ 2-‐phenyl-‐3-‐
methylaziridine 505.4850
O
N N
O
tBu tBu
tButBuCo
Cl
N
Ph Me
65
b (S,S)-‐dach (2R,3S)-‐ 2-‐phenyl-‐3-‐
methylaziridine 511.9451
O
N N
O
tBu tBu
tButBuCo
Cl
N
Me Ph
c (S,S)-‐DPEN (2S,3R)-‐ 2-‐phenyl-‐3-‐
methylaziridine 570.5242
O
N N
O
tBu tBu
tButBuCo
PhPh
Cl
N
Ph Me
d (S,S)-‐DPEN (2R,3S)-‐ 2-‐phenyl-‐3-‐
methylaziridine 576.8436
O
N N
O
tBu tBu
tButBuCo
PhPh
Cl
N
Me Ph
e (S,S)-‐Me-‐dach (2S,3R)-‐ 2-‐phenyl-‐3-‐
methylaziridine 656.4849
O
N N
O
tBu tBu
tButBuCo
Cl
N
MePh
f (S,S)-‐Me-‐dach (2R,3S)-‐ 2-‐phenyl-‐3-‐
methylaziridine 661.6967
O
N N
O
tBu tBu
tButBuCo
Cl
N
PhMe
g (S,S)-‐dach (2S,3R)-‐2-‐(4-‐chlorophenyl)-‐
3-‐methylaziridine 520.4126
O
N N
O
tBu tBu
tButBuCo
Cl
N
Me
Cl
66
h (S,S)-‐dach (2R,3S)-‐2-‐(4-‐chlorophenyl)-‐
3-‐methylaziridine 526.4416
O
N N
O
tBu tBu
tButBuCo
Cl
N
Me
Cl
i (S,S)-‐dach (1aS,7bS)-‐2,2-‐dimethyl-‐
1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine
568.8642
O
N N
O
tBu tBu
tButBuCo
Cl
N
O
j (S,S)-‐dach (1aR,7bR)-‐2,2-‐dimethyl-‐
1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine
573.6297
O
N N
O
tBu tBu
tButBuCo
Cl
N
O
k (S,S)-‐dach (1aS,7bS)-‐2,2-‐dimethyl-‐
1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine-‐6-‐carbonitrile
640.2074
O
N N
O
tBu tBu
tButBuCo
Cl
NH
ONC
l (S,S)-‐dach (1aR,7bR)-‐2,2-‐dimethyl-‐
1,1a,2,7b-‐
tetrahydrochromeno[3,4-‐
b]azirine-‐6-‐carbonitrile
646.1995
O
N N
O
tBu tBu
tButBuCo
Cl
N
O CN
m (S,S)-‐dach (1R,6R)-‐7-‐
azaspiro[bicyclo[4.1.0]hepta
ne-‐2,2'-‐[1,3]dioxolane]
544.3616
O
N N
O
tBu tBu
tButBuCo
Cl
N
O
O
67
n (S,S)-‐dach (1S,6S)-‐7-‐
azaspiro[bicyclo[4.1.0]hepta
ne-‐2,2'-‐[1,3]dioxolane]
544.1984
O
N N
O
tBu tBu
tButBuCo
Cl
NO
O
o (S,S)-‐dach methyl (2S,3S)-‐3-‐
phenylaziridine-‐2-‐
carboxylate
499.5152
O
N N
O
tBu tBu
tButBuCo
Cl
N
Ph CO2Me
p (S,S)-‐dach methyl (2R,3R)-‐3-‐
phenylaziridine-‐2-‐
carboxylate
514.5559
O
N N
O
tBu tBu
tButBuCo
Cl
N
MeO2C Ph
2.5.5 Alignment of Crystal Structure with Computed Structure
The computed structure geometry of the bis-(2R,3S)-2-phenyl-3-methylaziridine bound to the
salen cobalt complex was calculated by computing the Equilibrium Conformer using Molecular
Mechanics. Both the (R,R)- and (S,S)- catalysts were considered. The crystal structure
coordinates were loaded into Spartan. The catalyst was co-crystalized with formic acid and
methylene chloride, so these molecules were deleted. The computed structure was aligned to the
crystal structure using the Align function on Spartan ’08; the alignment was performed
considering all non-hydrogen atoms. The Alignment Score was returned by Spartan, and is
measured on a scale of 0 to 1 (a score of 1 represents an identical match). The RMSD for both
diastereomers was determined using VMD as follows. PDB structures for computed and crystal
structures were generated by Spartan following the alignment. The following code was used to
align the two structures in the VMD Tk Console:
set sel0 [atomselect 0 all]
set sel1 [atomselect 1 all]
set M [measure fit $sel0 $sel1]
$sel0 move $M
68
The RMSD was then returned using the RMSD Calculator function.
2.5.6 Energy Calculations on Manganese-Oxo Hybridization
The following manganese-oxo structure was drawn in Spartan.
O
N N
O
tBu tBu
Mn
Cl
O
The Equilibrium Conformer was found using Molecular Mechanics MMFF. Working off of that
structure, DFT B3LYP/6-31G* computation and basis set was used to find the Equilibrium
Geometry and corresponding energy for the following three multiplicity states: singlet, triplet
and quintet. A neutral charge was assigned to all three species. The absolute energies (in
Hartrees) for the three species appear in the Table below. The manganese-oxo bond distance was
measured; as well, the partial charge on the oxygen atom (i.e. Mn=O) was determined. These
values appear in the text body.
Table 6:
Entry Multuplicity Energy (Ha)
O
N N
O
tBu tBu
Mn
Cl
O
a Singlet -‐3035.023040
b Triplet -‐3035.045152
c Quintet -‐3035.041359
The equilibrium geometries and energies for cis-2-butene and cis-2,3-epoxybutane were
calculated using DFT B3LYP/6-31G* as model olefin and epoxide substrates.
Table 7:
Entry Compound Energy (Ha)
69
a cis-‐2-‐butene -‐157.224760
b 2,3-‐dimethyloxirane -‐232.428509
The energies for the different multiplicity states of the catalyst lacking the oxygen is shown as
well.
Table 8:
Entry Multuplicity Energy (Ha)
O
N
tBu
N
O
tBu
Mn
Cl
a Singlet -‐2959.837978
b Triplet -‐2959.879385
c Quintet -‐2959.917029
2.5.7 Calculation of Predicted Enantiomer Excess
The difference in energy, ∆G, for the two cis-diastereomer was determined. The ee was
determined as follows:
; with
70
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74
Appendix A: 1H and 13C NMR Spectra
N
N
MeO
MeO HO
HO 1H-NMR
13C-NMR
75
N
N
Me2N
Me2N HO
HO 1H-NMR
13C-NMR
76
N
N
F
F HO
HO 1H-NMR
13C-NMR
77
NH3H3N
OMeMeO
Cl Cl
1H-NMR
13C-NMR
78
NH3H3N
NHMe2Me2HN
Cl Cl
ClCl 1H-NMR
13C-NMR
79
H3N NH3
FF
ClCl
1H-NMR
13C-NMR
80
HNH2N SO
O
1H-NMR
13C-NMR
81
HNH2N SO
O
OMeMeO 1H-NMR
13C-NMR
82
HNH2N
NMe2Me2N
SO
O
1H-NMR
13C-NMR
83
HNH2N SO
O
FF 1H-NMR
13C-NMR
84
Appendix B: Cartesian Coordinates of Computed Complexes Chapter 1 Table 1, Entry a H 3.781091 -2.369029 -1.130808 C 3.795989 -1.326742 -0.831405 C 3.731398 1.412063 -0.018580 C 3.767773 -0.978550 0.546575 C 3.633437 -0.303647 -1.796352 C 3.593950 1.073624 -1.389499 C 3.786839 0.396549 0.955981 H 3.753044 -1.759313 1.299360 H 3.524958 -0.556939 -2.845490 H 3.435810 1.851414 -2.127733 H 3.762352 0.646632 2.010351 H 3.628923 2.446838 0.289114 Ru 1.975304 -0.050300 -0.354707 N 0.445541 -1.144078 -0.750737 H 0.443322 -2.029141 -1.256395 C -0.736356 0.643360 0.309728 O 0.525747 1.239572 0.109112 H -0.786248 0.199954 1.322071 C -0.889332 -0.528178 -0.694733 H -1.132972 -0.099708 -1.682565 C -1.848390 1.672458 0.185658 C -3.925753 3.547546 -0.087888 C -1.722656 2.750578 -0.699346 C -3.023449 1.551507 0.936912 C -4.057805 2.478789 0.800175 C -2.753096 3.681222 -0.835077 H -0.799422 2.857442 -1.260188 H -3.128926 0.723873 1.634548 H -4.963192 2.369140 1.392287 H -2.639063 4.517152 -1.521528 H -4.727282 4.274748 -0.192054 C -1.973907 -1.528669 -0.339799 C -3.999766 -3.363285 0.331509 C -1.799776 -2.432700 0.718985 C -3.176456 -1.562177 -1.057471 C -4.183491 -2.469623 -0.724630 C -2.803419 -3.342002 1.052521 H -0.864980 -2.420652 1.272742 H -3.323776 -0.867365 -1.881001 H -5.109853 -2.480246 -1.293386 H -2.651321 -4.036862 1.874866 H -4.780971 -4.073973 0.588767 Lig 3.718231 0.045549 -0.422213 Table 1, Entry b H 4.554750 -2.411839 -1.104531 C 4.576554 -1.370637 -0.801700 C 4.529021 1.366115 0.018958 C 4.528277 -1.026412 0.576757
C 4.440731 -0.342863 -1.765770 C 4.410234 1.033489 -1.354946 C 4.555166 0.347312 0.990821 H 4.493529 -1.809172 1.326886 H 4.347402 -0.591404 -2.817542 H 4.274654 1.815222 -2.093536 H 4.515840 0.594537 2.045429 H 4.433739 2.401121 0.328220 Ru 2.761227 -0.076860 -0.351535 N 1.229841 -1.156636 -0.773044 H 1.226318 -2.043283 -1.276019 C 0.046266 0.636825 0.276595 O 1.316663 1.224463 0.095679 H -0.019597 0.190877 1.287220 C -0.101719 -0.530353 -0.731764 H -0.329367 -0.098130 -1.722016 C -1.054406 1.674925 0.143918 C -3.118255 3.574177 -0.144640 C -2.236206 1.571856 0.878589 C -0.918791 2.757470 -0.738607 C -1.932681 3.695961 -0.883801 C -3.269953 2.504085 0.742496 H -2.362650 0.747151 1.576174 H 0.007335 2.862826 -1.294958 H -1.828864 4.540386 -1.559129 H -4.171737 2.387916 1.333439 C -1.195190 -1.525397 -0.395968 C -3.241620 -3.362163 0.239192 C -2.367706 -1.590985 -1.151802 C -1.066174 -2.405877 0.692777 C -2.070065 -3.310734 1.009847 C -3.390324 -2.495366 -0.847896 H -2.493593 -0.919024 -1.997605 H -0.157713 -2.379149 1.288231 H -1.971887 -3.993892 1.848238 H -4.284065 -2.515996 -1.461292 O -4.165971 -4.292139 0.628005 C -5.362371 -4.399876 -0.124057 H -5.938758 -3.465021 -0.105173 H -5.945571 -5.191830 0.349941 H -5.161297 -4.674180 -1.168684 O -4.055667 4.551226 -0.356599 C -5.266695 4.479680 0.372996 H -5.823017 3.558411 0.150588 H -5.859717 5.341200 0.058404 H -5.092982 4.537399 1.456365 Lig 4.506664 0.001167 -0.389313 Table 1, Entry c H 4.844260 -2.418594 -1.123402 C 4.858023 -1.390018 -0.779758 C 4.785008 1.312279 0.150433
85
C 4.786218 -1.100482 0.610638 C 4.733748 -0.324884 -1.704084 C 4.688706 1.033640 -1.238032 C 4.802570 0.254902 1.080928 H 4.744997 -1.912535 1.328654 H 4.660236 -0.530212 -2.766745 H 4.560249 1.844000 -1.946565 H 4.746188 0.458411 2.143998 H 4.678102 2.333617 0.498671 Ru 3.029869 -0.119638 -0.309297 N 1.505864 -1.167672 -0.826762 H 1.514174 -2.016414 -1.391728 C 0.302531 0.567101 0.290312 O 1.578956 1.162244 0.168337 H 0.218562 0.054435 1.267683 C 0.179130 -0.529710 -0.794442 H 0.000391 -0.024486 -1.760385 C -0.792290 1.613758 0.208141 C -2.875677 3.558872 0.017841 C -0.669506 2.730567 -0.624959 C -1.968704 1.496309 0.952986 C -2.990222 2.439391 0.869317 C -1.677864 3.685603 -0.719905 H 0.249511 2.863012 -1.188370 H -2.094538 0.646752 1.620801 H -3.874866 2.298020 1.479395 H -1.521368 4.539645 -1.369044 C -0.941353 -1.526115 -0.578377 C -3.079940 -3.382261 -0.170270 C -0.857382 -2.537125 0.388224 C -2.120213 -1.461195 -1.329304 C -3.169950 -2.353104 -1.133085 C -1.894035 -3.442647 0.595754 H 0.044399 -2.620430 0.989817 H -2.228706 -0.685341 -2.083972 H -4.060573 -2.244052 -1.740649 H -1.773716 -4.200290 1.361164 N -4.109855 -4.308451 0.002121 N -3.907787 4.497661 -0.095155 C -4.971416 4.481987 0.893805 H -5.514937 3.530709 0.866765 H -5.686788 5.273331 0.658636 H -4.609988 4.636463 1.924910 C -3.622536 5.771777 -0.732124 H -3.316649 5.626961 -1.774481 H -2.828889 6.345045 -0.223080 H -4.532310 6.376758 -0.739763 C -4.079206 -5.184333 1.160316 H -3.178019 -5.808302 1.152906 H -4.940758 -5.855010 1.124639 H -4.105109 -4.638889 2.118773 C -5.404057 -4.035202 -0.598765 H -5.323603 -3.974374 -1.690211 H -5.858034 -3.096653 -0.239433 H -6.085318 -4.856885 -0.367238 Lig 4.775712 -0.035760 -0.313312
Table 1, Entry d H 4.176689 -2.365086 -1.150546 C 4.188838 -1.324833 -0.844183 C 4.118413 1.408682 -0.013215 C 4.164888 -0.985346 0.536007 C 4.020559 -0.295968 -1.802073 C 3.977169 1.078283 -1.385946 C 4.180910 0.387089 0.954247 H 4.154915 -1.770769 1.283963 H 3.909413 -0.541978 -2.852635 H 3.813789 1.860261 -2.118588 H 4.159557 0.630173 2.010324 H 4.014166 2.441167 0.301358 Ru 2.366212 -0.057069 -0.353621 N 0.837680 -1.154543 -0.752775 H 0.838025 -2.031941 -1.271614 C -0.344338 0.621688 0.322739 O 0.911851 1.226697 0.118317 H -0.385384 0.167005 1.330817 C -0.497259 -0.540426 -0.692041 H -0.742706 -0.102515 -1.675470 C -1.460846 1.647633 0.219901 C -3.519615 3.508535 -0.006024 C -1.346010 2.736179 -0.654155 C -2.628010 1.519574 0.982287 C -3.667762 2.444197 0.874270 C -2.372262 3.673026 -0.773542 H -0.429681 2.851714 -1.223851 H -2.728275 0.686021 1.672944 H -4.575085 2.354893 1.463162 H -2.292736 4.525919 -1.440617 C -1.581943 -1.543200 -0.345322 C -3.591731 -3.359054 0.313030 C -1.407613 -2.457360 0.705133 C -2.788065 -1.568792 -1.058125 C -3.801386 -2.472288 -0.735414 C -2.407198 -3.369027 1.041529 H -0.471384 -2.454963 1.255740 H -2.939294 -0.869070 -1.876205 H -4.737948 -2.498621 -1.282975 H -2.281949 -4.081871 1.850347 F -4.563284 -4.243015 0.631475 F -4.517229 4.417298 -0.111760 Lig 4.108463 0.044651 -0.425860 Table 1, Entry e H 3.610935 -2.201180 -1.484986 C 3.685494 -1.188121 -1.099908 C 3.745213 1.422769 -0.072982 C 4.209588 -0.981314 0.201953 C 3.412421 -0.078467 -1.981552 C 3.424753 1.208903 -1.460739 C 4.203771 0.346140 0.726731 H 4.521326 -1.818503 0.815446 H 3.116423 -0.259338 -3.009868 H 3.115031 2.051733 -2.070487 H 4.499287 0.525546 1.754464
86
H 3.673293 2.417763 0.350330 Ru 2.127883 -0.118173 0.111845 H 1.794641 -0.428384 1.644566 N 0.443002 -1.458426 -0.171271 H 0.553640 -2.145846 -0.916859 H 0.353933 -1.993801 0.690917 C -0.662036 0.622846 0.464842 O 0.564749 1.190072 0.173918 H -0.738656 0.310811 1.527849 C -0.818925 -0.672722 -0.397102 H -0.787071 -0.347078 -1.442094 C -1.795198 1.604699 0.177541 C -3.884593 3.389359 -0.417962 C -1.645391 2.566565 -0.828570 C -2.999579 1.556323 0.889197 C -4.039284 2.439212 0.593022 C -2.681955 3.452019 -1.125511 H -0.696728 2.618469 -1.352838 H -3.124414 0.821938 1.681313 H -4.967810 2.388706 1.156680 H -2.549178 4.196949 -1.906775 H -4.691831 4.080942 -0.646439 C -2.055293 -1.511941 -0.162962 C -4.358679 -3.081614 0.244332 C -2.296885 -2.127711 1.076046 C -2.992705 -1.692168 -1.188215 C -4.134797 -2.468405 -0.988989 C -3.436106 -2.906822 1.277968 H -1.597567 -1.987855 1.898366 H -2.827465 -1.211479 -2.149546 H -4.848962 -2.594671 -1.798528 H -3.604886 -3.374556 2.244468 H -5.246121 -3.689091 0.400486 Lig 3.780207 0.121652 -0.614416 Table 1, Entry f H 4.418719 -2.160591 -1.503228 C 4.470160 -1.215002 -0.971243 C 4.449204 1.220184 0.425389 C 4.854041 -1.208129 0.394607 C 4.297277 0.017746 -1.701698 C 4.273770 1.217712 -1.004824 C 4.816858 0.032608 1.102788 H 5.092003 -2.132502 0.907760 H 4.107084 -0.007009 -2.770175 H 4.043481 2.147023 -1.515855 H 5.010413 0.056159 2.169413 H 4.340622 2.145215 0.979639 Ru 2.806273 -0.292261 0.234302 H 2.331224 -0.866201 1.649781 N 1.122643 -1.492098 -0.430428 H 1.273414 -1.973253 -1.316789 H 0.992095 -2.224474 0.265343 C 0.025416 0.459599 0.565700 O 1.274367 1.035407 0.420540 H -0.094121 -0.031752 1.553569 C -0.131225 -0.659660 -0.512833
H -0.091459 -0.157394 -1.485061 C -1.072933 1.506531 0.419862 C -3.097428 3.442323 0.096128 C -0.888636 2.606953 -0.419754 C -2.291937 1.397398 1.103525 C -3.294898 2.346644 0.947326 C -1.885080 3.572402 -0.589940 H 0.064430 2.715528 -0.927886 H -2.459479 0.554661 1.769723 H -4.237804 2.265669 1.479878 H -1.702080 4.416469 -1.246313 C -1.376709 -1.510989 -0.420328 C -3.708470 -3.098592 -0.240872 C -1.643311 -2.286004 0.715577 C -2.310751 -1.550655 -1.467509 C -3.459070 -2.327711 -1.385274 C -2.790660 -3.076236 0.815938 H -0.952602 -2.273229 1.556556 H -2.137708 -0.952697 -2.359391 H -4.182092 -2.352761 -2.194802 H -2.957530 -3.657042 1.716122 O -4.862484 -3.827709 -0.254055 C -5.171521 -4.611942 0.886737 H -4.410597 -5.383678 1.065084 H -6.127352 -5.092461 0.669972 H -5.273685 -3.992229 1.787348 O -4.141558 4.325774 0.012535 C -3.988913 5.459956 -0.820478 H -3.154119 6.095723 -0.494541 H -4.921498 6.022329 -0.738056 H -3.830749 5.176269 -1.870240 Lig 4.526885 0.010853 -0.292497 Table 1, Entry g H 4.849246 -2.100307 -1.279569 C 4.877316 -1.150973 -0.752031 C 4.796605 1.290498 0.631811 C 5.253944 -1.130530 0.616229 C 4.688598 0.073660 -1.492292 C 4.631352 1.275136 -0.798626 C 5.176855 0.110689 1.317776 H 5.508037 -2.047060 1.135674 H 4.507870 0.040490 -2.561972 H 4.381172 2.196322 -1.315193 H 5.357527 0.142832 2.386539 H 4.666267 2.216115 1.180166 Ru 3.183906 -0.255594 0.421313 H 2.685434 -0.790467 1.845898 N 1.556228 -1.527001 -0.238218 H 1.755637 -2.056073 -1.086900 H 1.406569 -2.219760 0.493304 C 0.368673 0.445297 0.600050 O 1.616589 1.036635 0.501959 H 0.192697 0.004578 1.603252 C 0.288937 -0.730317 -0.425170 H 0.363770 -0.280963 -1.421036 C -0.727738 1.469356 0.332873
87
C -2.766262 3.378345 -0.242440 C -0.510144 2.513816 -0.575465 C -1.976584 1.402702 0.950343 C -2.978916 2.336747 0.678301 C -1.502034 3.442171 -0.864771 H 0.464186 2.592449 -1.047765 H -2.177945 0.610325 1.667985 H -3.922116 2.254302 1.206725 H -1.298298 4.216113 -1.598436 C -0.940862 -1.603303 -0.343879 C -3.286513 -3.236597 -0.175632 C -1.241972 -2.340056 0.811508 C -1.844792 -1.698613 -1.407800 C -2.991050 -2.484488 -1.334155 C -2.378569 -3.136136 0.903116 H -0.585495 -2.284520 1.678236 H -1.659796 -1.129253 -2.316308 H -3.658250 -2.505415 -2.187505 H -2.559413 -3.673150 1.826716 N -4.415561 -4.049937 -0.100532 N -3.776790 4.308461 -0.581113 C -5.095779 4.106602 -0.010888 H -5.431970 3.081697 -0.192645 H -5.799496 4.785292 -0.504337 H -5.145749 4.301217 1.076764 C -3.406317 5.718059 -0.641780 H -2.469534 5.854192 -1.182709 H -3.289655 6.170225 0.359887 H -4.184816 6.272138 -1.177949 C -4.809490 -4.580794 1.193901 H -4.025860 -5.227251 1.605210 H -5.705232 -5.192952 1.071037 H -5.026083 -3.794198 1.935393 C -5.453226 -3.901853 -1.107816 H -5.065081 -4.135057 -2.105848 H -5.882312 -2.886787 -1.138048 H -6.258197 -4.609145 -0.897324 Lig 4.904112 0.078080 -0.079522 Table 1, Entry h H 4.068316 -2.180440 -1.447953 C 4.129124 -1.217672 -0.948673 C 4.135718 1.262007 0.365495 C 4.536765 -1.166528 0.408954 C 3.943031 -0.010532 -1.717113 C 3.933373 1.212107 -1.059819 C 4.513821 0.097061 1.075555 H 4.783912 -2.073156 0.948632 H 3.734478 -0.071604 -2.780604 H 3.695873 2.124868 -1.596734 H 4.727105 0.156832 2.136942 H 4.040651 2.205369 0.890495 Ru 2.486721 -0.251153 0.254232 H 2.036881 -0.769058 1.699973 N 0.789273 -1.476014 -0.333467 H 0.929846 -2.000233 -1.196624 H 0.666600 -2.171871 0.400136
C -0.289813 0.522752 0.586532 O 0.957105 1.087430 0.408538 H -0.407604 0.074242 1.594927 C -0.458432 -0.641471 -0.444388 H -0.421489 -0.180439 -1.436701 C -1.386473 1.567020 0.398989 C -3.380990 3.467203 -0.010250 C -1.185758 2.634564 -0.485280 C -2.605778 1.482185 1.080703 C -3.613096 2.427398 0.881164 C -2.179292 3.589990 -0.697941 H -0.226643 2.716106 -0.985897 H -2.775176 0.667120 1.779504 H -4.560456 2.372287 1.407862 H -2.033088 4.425290 -1.375904 C -1.711563 -1.476853 -0.309995 C -4.032456 -3.007168 -0.058783 C -1.962777 -2.222294 0.854418 C -2.660295 -1.520607 -1.340285 C -3.824113 -2.280921 -1.224570 C -3.117675 -2.991180 0.988134 H -1.255443 -2.197945 1.680701 H -2.491900 -0.943249 -2.245915 H -4.563428 -2.315376 -2.018258 H -3.318326 -3.567021 1.885840 F -5.153659 -3.747760 0.064082 F -4.349784 4.391811 -0.208011 Lig 4.198639 0.029407 -0.312600 Table 1, Entry i C -0.654873 0.036044 0.000000 H -1.017141 0.568882 -0.893118 H -1.017141 0.568882 0.893118 H -1.095539 -0.964597 0.000000 O 0.753064 -0.138353 0.000000 H 1.158065 0.741499 0.000000 Table 1, Entry j C 0.000000 0.000000 0.530643 H 0.937819 0.000000 1.125678 H -0.937819 0.000000 1.125678 O 0.000000 0.000000 -0.675892 Table 2, Entry a H 2.634854 -0.308157 2.847688 C 3.091086 -0.397406 1.867620 C 4.171745 -0.615667 -0.745300 C 3.656908 0.752259 1.224557 C 3.096986 -1.649208 1.193326 C 3.672466 -1.773583 -0.105226 C 4.206479 0.644878 -0.071203 H 3.613878 1.719791 1.714060 H 2.601125 -2.502918 1.642817 H 3.613955 -2.714597 -0.639260 H 4.569386 1.526931 -0.586351 H 4.507144 -0.676211 -1.775665
88
Ru 2.054609 -0.162945 -0.065663 H 1.653999 0.454261 -1.882486 N 0.549376 1.235846 0.246773 H 0.739193 1.930083 0.972047 H 0.500785 1.830140 -0.814665 C -0.778244 -0.651737 -0.417418 O 0.444784 -1.330141 -0.276612 H -0.892832 -0.237944 -1.435197 C -0.745236 0.554802 0.554236 H -0.667223 0.134860 1.566954 C -1.936415 -1.601773 -0.152489 C -4.082942 -3.342225 0.362869 C -1.789422 -2.668193 0.743080 C -3.170190 -1.420872 -0.789899 C -4.237736 -2.281705 -0.532636 C -2.854203 -3.532648 0.999393 H -0.823806 -2.822379 1.214606 H -3.295893 -0.597144 -1.488311 H -5.188738 -2.127380 -1.037065 H -2.722569 -4.361323 1.691849 H -4.911508 -4.018354 0.558595 C -1.950346 1.475907 0.514229 C -4.239529 3.110851 0.481321 C -2.239008 2.273600 -0.605324 C -2.821361 1.514592 1.612178 C -3.958723 2.322914 1.598290 C -3.375802 3.082949 -0.615928 H -1.556304 2.279034 -1.451886 H -2.611217 0.897516 2.483546 H -4.622005 2.336485 2.459378 H -3.584510 3.698235 -1.487649 H -5.123399 3.743586 0.466739 C 1.283362 1.294894 -2.643251 H 0.730935 0.682430 -3.382928 H 2.243783 1.622971 -3.086290 O 0.577249 2.246477 -2.023010 Lig 3.649278 -0.506454 0.560629 Table 2, Entry b H -3.136834 0.793770 2.817973 C -3.666884 0.598973 1.892309 C -4.923576 0.058836 -0.589051 C -4.132699 -0.722752 1.588198 C -3.875390 1.645321 0.949089 C -4.527333 1.389898 -0.285462 C -4.787814 -0.990577 0.363755 H -3.939785 -1.532770 2.284429 H -3.450157 2.625358 1.137568 H -4.612789 2.170991 -1.031317 H -5.081834 -2.001826 0.107948 H -5.322770 -0.166886 -1.572723 Ru -2.738700 -0.008368 -0.007216 H -2.361076 -0.794886 -1.780117 N -1.157507 -1.300625 0.390300 H -1.278546 -1.906241 1.204064 H -1.134940 -2.012601 -0.595224 C 0.039642 0.539652 -0.574646
O -1.200748 1.191574 -0.426130 H 0.095077 0.002977 -1.538371 C 0.116459 -0.532459 0.539345 H 0.061615 0.014009 1.491786 C 1.169222 1.552437 -0.523423 C 3.268444 3.430080 -0.418829 C 1.068748 2.698263 0.266983 C 2.344423 1.363034 -1.265550 C 3.384553 2.282866 -1.215827 C 2.102446 3.636859 0.326496 H 0.154129 2.869754 0.825763 H 2.446205 0.478042 -1.888902 H 4.293633 2.138963 -1.792042 H 1.983338 4.520072 0.944619 C 1.357098 -1.402673 0.563178 C 3.711624 -2.951374 0.654178 C 1.620214 -2.365734 -0.419866 C 2.299448 -1.230917 1.589866 C 3.461910 -1.988641 1.641364 C 2.784442 -3.137771 -0.377901 H 0.897413 -2.531642 -1.215090 H 2.121356 -0.483032 2.359386 H 4.190451 -1.854738 2.435093 H 2.952562 -3.880950 -1.149369 C -2.003067 -1.715977 -2.444297 H -1.501408 -1.190429 -3.280784 H -2.971483 -2.119526 -2.799537 O -1.241869 -2.567975 -1.746830 O 4.338723 4.284212 -0.441916 C 4.249043 5.479391 0.312317 H 3.414007 6.109233 -0.024773 H 5.189302 6.010476 0.148930 H 4.131351 5.275562 1.385495 O 4.875738 -3.655076 0.793541 C 5.195537 -4.617563 -0.196771 H 4.441210 -5.414165 -0.246162 H 6.154331 -5.047292 0.099966 H 5.295513 -4.157639 -1.189027 Lig -4.318949 0.329950 0.653140 Table 2, Entry c H -3.700196 0.210474 2.742711 C -4.143260 0.309318 1.757522 C -5.184695 0.551306 -0.868605 C -4.719517 -0.830100 1.107189 C -4.122175 1.564529 1.087660 C -4.682823 1.700171 -0.217551 C -5.239395 -0.712636 -0.199294 H -4.694417 -1.799843 1.593286 H -3.624857 2.411462 1.547963 H -4.604624 2.641790 -0.747934 H -5.599727 -1.589569 -0.724872 H -5.503506 0.618114 -1.903579 Ru -3.082716 0.073331 -0.156469 H -2.671625 -0.625216 -1.962087 N -1.580736 -1.314768 0.215767 H -1.772208 -1.970857 0.975028
89
H -1.543004 -1.957923 -0.814306 C -0.254715 0.530726 -0.547634 O -1.476625 1.225464 -0.418815 H -0.164724 0.063071 -1.544373 C -0.280039 -0.624598 0.482907 H -0.353327 -0.155379 1.474843 C 0.900213 1.494711 -0.365244 C 3.080985 3.307759 -0.013074 C 0.887348 2.460896 0.646087 C 2.015598 1.463408 -1.205257 C 3.082246 2.343886 -1.043876 C 1.942889 3.350167 0.822627 H 0.016494 2.536947 1.291212 H 2.054721 0.738800 -2.015664 H 3.914391 2.274879 -1.734691 H 1.869239 4.086939 1.613902 C 0.921118 -1.546917 0.487257 C 3.253664 -3.196960 0.525159 C 1.186775 -2.451105 -0.551728 C 1.845977 -1.483032 1.536414 C 2.989437 -2.275033 1.561037 C 2.321996 -3.256044 -0.534700 H 0.489015 -2.535328 -1.381230 H 1.680335 -0.783437 2.353664 H 3.672525 -2.176939 2.396386 H 2.481638 -3.932035 -1.366206 C -2.300591 -1.498823 -2.677857 H -1.716865 -0.930491 -3.429837 H -3.255626 -1.825519 -3.134457 O -1.631610 -2.441408 -2.002608 N 4.380226 -4.023849 0.561721 N 4.164218 4.175377 0.177485 C 3.981034 5.337946 1.030818 H 3.682395 5.036285 2.040539 H 3.223921 6.044732 0.648399 H 4.933187 5.867771 1.117474 C 5.122552 4.327450 -0.905437 H 4.667509 4.702234 -1.838156 H 5.615439 3.375407 -1.128070 H 5.898479 5.031305 -0.595511 C 4.700206 -4.818808 -0.611610 H 3.861223 -5.471803 -0.873654 H 5.555595 -5.460276 -0.384448 H 4.948850 -4.211089 -1.498574 C 5.493600 -3.636075 1.413692 H 5.205493 -3.644134 2.471014 H 5.885716 -2.632947 1.177273 H 6.303852 -4.358938 1.293044 Lig -4.681977 0.430431 0.444487 Table 2, Entry d H -3.367558 -0.916284 2.644423 C -3.668142 -0.350247 1.768246 C -4.335536 1.128833 -0.568340 C -4.321575 -1.009244 0.691593 C -3.372849 1.048110 1.696203 C -3.739971 1.784030 0.526301
C -4.574709 -0.283177 -0.496037 H -4.494091 -2.078998 0.724765 H -2.863918 1.543098 2.515570 H -3.452799 2.826663 0.440645 H -4.948070 -0.804477 -1.371403 H -4.524306 1.665051 -1.491077 Ru -2.398525 0.045224 0.001158 H -1.981621 -0.769207 -1.756673 N -0.834833 -1.260990 0.440837 H -0.973317 -1.840990 1.270136 H -0.833807 -1.999406 -0.513499 C 0.383310 0.570517 -0.530526 O -0.848956 1.233268 -0.386347 H 0.441648 0.041967 -1.498638 C 0.451521 -0.512339 0.576752 H 0.419108 0.024707 1.535081 C 1.520560 1.575933 -0.462965 C 3.603019 3.416929 -0.324184 C 1.422950 2.701905 0.363687 C 2.684245 1.396849 -1.219920 C 3.735326 2.311990 -1.155506 C 2.461452 3.629397 0.439728 H 0.510616 2.858278 0.929730 H 2.773467 0.528308 -1.867070 H 4.639941 2.183987 -1.741237 H 2.395358 4.511585 1.068839 C 1.687959 -1.392368 0.563165 C 4.023483 -2.909850 0.546558 C 1.905365 -2.354777 -0.437737 C 2.668624 -1.213527 1.549274 C 3.842638 -1.966638 1.550115 C 3.072417 -3.118255 -0.445693 H 1.144578 -2.522027 -1.196965 H 2.519321 -0.466597 2.325410 H 4.607233 -1.832072 2.308402 H 3.249723 -3.870650 -1.207665 C -1.681027 -1.735978 -2.384065 H -1.162392 -1.275355 -3.247847 H -2.673688 -2.101438 -2.713162 O -0.958396 -2.595407 -1.656642 F 5.154910 -3.649439 0.538444 F 4.609912 4.317891 -0.263183 Lig -4.002130 0.386384 0.60299
Chapter 2 Table 1, Entry a Mn -0.246146 0.342838 -0.690074 N -1.327316 2.166623 -0.612878 N -1.804006 -0.111647 -2.061072 C -0.728939 3.238603 -0.212743 H -1.323226 4.168123 -0.234035 C -1.968913 -1.327226 -2.458805 H -2.774773 -1.508044 -3.190750 C 0.681215 3.376020 0.223790 C 3.275424 4.012577 1.022282 C 1.594117 2.345622 0.515244
90
C 1.089762 4.714991 0.345861 C 2.386836 5.062694 0.746122 C 2.921569 2.647639 0.920422 H 0.396744 5.527152 0.121004 H 4.285774 4.275793 1.326488 C -1.213342 -2.513375 -2.003529 C 0.024496 -4.933676 -1.423374 C -1.883062 -3.726165 -2.221891 C 0.079833 -2.517918 -1.452611 C 0.755882 -3.741496 -1.214471 C -1.293645 -4.957592 -1.908077 H -2.882197 -3.735154 -2.660943 H 0.507644 -5.890080 -1.234231 C -2.696529 2.036629 -1.235392 H -3.306114 1.529419 -0.474936 C -2.548365 1.129142 -2.496176 H -1.902903 1.612343 -3.241706 O 1.273198 1.016063 0.503098 O 0.776492 -1.380044 -1.160482 C -3.919186 0.849122 -3.104539 H -3.825628 0.254491 -4.020728 H -4.540822 0.271426 -2.408363 C -3.352516 3.361424 -1.607985 H -2.716287 3.928313 -2.299755 H -3.500509 3.986421 -0.719349 C -4.715434 3.113263 -2.259705 H -5.146607 4.067609 -2.582742 H -5.400475 2.691844 -1.513362 C -4.627348 2.161566 -3.452048 H -5.635181 1.946445 -3.824973 H -4.086318 2.657260 -4.267824 C 3.984803 1.551874 1.233544 C 2.262847 -3.820970 -0.816625 C 3.530352 0.685564 2.429601 H 4.308582 -0.032529 2.714596 H 2.633953 0.098369 2.217888 H 3.315470 1.308483 3.305881 C 4.217900 0.661398 -0.008359 H 5.011570 -0.072589 0.175490 H 4.516998 1.265555 -0.873087 H 3.332683 0.091936 -0.300330 C 2.520623 -3.144683 0.544901 H 1.876644 -3.567497 1.323486 H 2.353876 -2.066288 0.518043 H 3.560287 -3.283714 0.865166 C 3.128706 -3.141960 -1.903784 H 2.944243 -3.588293 -2.888164 H 4.197188 -3.252805 -1.683406 H 2.939813 -2.068221 -1.990345 C 2.807968 -5.267778 -0.681748 H 2.717129 -5.825016 -1.621536 H 2.286141 -5.824628 0.105377 H 3.872514 -5.266937 -0.416585 C 5.380630 2.109587 1.620515 H 6.089560 1.296820 1.821505 H 5.335118 2.721177 2.529272 H 5.812795 2.714828 0.814969
O -1.329300 -0.699731 1.110783 C -0.447588 -1.288055 1.929881 C -1.168386 0.012300 2.248708 H 0.616061 -1.242704 1.756077 H -0.542846 0.898241 2.232954 C -0.883593 -2.612254 2.465624 H -1.967729 -2.690150 2.603089 H -0.404881 -2.797636 3.432417 H -0.579904 -3.412429 1.783238 C -2.223502 0.064649 3.327110 C -4.150057 0.172301 5.388531 C -3.591576 0.233056 3.038454 C -1.852576 -0.032256 4.681361 C -2.804915 0.017499 5.700400 C -4.544238 0.282089 4.059807 H -3.962725 0.329919 2.022981 H -0.808964 -0.148740 4.975731 H -2.500993 -0.062146 6.744420 H -5.602739 0.407490 3.832517 C -2.065621 -6.275836 -2.151057 C -1.307757 -7.545730 -1.701356 H -1.065685 -7.513051 -0.632650 H -0.374670 -7.680079 -2.260764 H -1.911364 -8.445936 -1.868954 C -3.398342 -6.248075 -1.369990 H -3.223169 -6.101030 -0.297605 H -3.948007 -7.188757 -1.492421 H -4.062972 -5.445749 -1.707971 C -2.361538 -6.427810 -3.658313 H -1.434802 -6.423664 -4.244300 H -2.994772 -5.619400 -4.039874 H -2.883276 -7.369420 -3.865634 C 2.794772 6.549824 0.861737 C 4.253548 6.773491 1.321517 H 4.486514 7.843020 1.389683 H 4.970645 6.333675 0.618602 H 4.435179 6.341572 2.312592 C 2.642236 7.235400 -0.513558 H 2.957737 8.284414 -0.469434 H 1.606099 7.228307 -0.868902 H 3.253963 6.734604 -1.273329 C 1.883221 7.257836 1.887915 H 2.173466 8.307186 2.016631 H 1.943374 6.772193 2.869134 H 0.831229 7.253165 1.582743 Cl 0.820626 1.296736 -2.476044 H -4.891776 0.210953 6.186496 Table1, Entry b Mn -0.385394 0.705319 -0.552167 N -1.336130 2.584472 -0.297710 N -2.015526 0.463237 -1.894024 C -0.650497 3.582874 0.150047 H -1.178892 4.549264 0.217141 C -2.271754 -0.701914 -2.383129 H -3.108941 -0.769677 -3.098918 C 0.780506 3.594230 0.537229 C 3.438933 3.994445 1.275279
91
C 1.627692 2.486214 0.722094 C 1.286689 4.890362 0.732959 C 2.618176 5.119667 1.104722 C 2.985958 2.667378 1.095553 H 0.645758 5.761663 0.589955 H 4.475233 4.165949 1.556957 C -1.585171 -1.967381 -2.050404 C -0.507400 -4.504028 -1.694187 C -2.346348 -3.111176 -2.333786 C -0.279652 -2.102252 -1.547019 C 0.313981 -3.384408 -1.425586 C -1.838671 -4.400428 -2.129200 H -3.356776 -3.017713 -2.735750 H -0.088766 -5.502921 -1.589822 C -2.732745 2.591513 -0.871023 H -3.346811 2.065579 -0.126998 C -2.690245 1.779464 -2.202371 H -2.040699 2.277937 -2.934195 O 1.213059 1.186315 0.630464 O 0.502743 -1.040463 -1.191357 C -4.097447 1.636473 -2.774491 H -4.076292 1.112094 -3.736931 H -4.731031 1.045729 -2.100396 C -3.311965 3.980771 -1.113878 H -2.664771 4.558898 -1.785919 H -3.385614 4.541707 -0.174649 C -4.710843 3.872354 -1.726373 H -5.088756 4.874809 -1.957262 H -5.395334 3.437463 -0.987311 C -4.728801 3.014639 -2.990913 H -5.761353 2.894190 -3.337910 H -4.185455 3.538166 -3.787542 C 3.978440 1.481889 1.293116 C 1.821795 -3.600137 -1.086179 C 3.503197 0.566308 2.443630 H 4.237595 -0.221581 2.649581 H 2.561077 0.058020 2.226324 H 3.361771 1.139031 3.367773 C 4.106839 0.667325 -0.014374 H 4.852367 -0.130152 0.088904 H 4.418977 1.309085 -0.846795 H 3.174413 0.181450 -0.310426 C 2.164367 -3.057071 0.315151 H 1.507712 -3.490610 1.076929 H 2.083172 -1.970328 0.375803 H 3.197188 -3.300172 0.592543 C 2.703585 -2.896106 -2.144135 H 2.460791 -3.247113 -3.154126 H 3.767115 -3.097698 -1.968738 H 2.589368 -1.808451 -2.139043 C 2.265849 -5.087281 -1.084991 H 2.106152 -5.559317 -2.061535 H 1.730407 -5.668469 -0.325024 H 3.335424 -5.181224 -0.859692 C 5.422173 1.914120 1.664404 H 6.077827 1.042598 1.783298 H 5.449789 2.462248 2.613480
H 5.869716 2.543248 0.886017 O -1.471853 -0.402379 1.218749 C -0.591607 -1.133438 1.938163 C -1.196728 0.187022 2.391078 H 0.457031 -1.090925 1.668162 H -0.530734 1.031682 2.484401 C -0.976518 -2.424236 2.621151 C -1.655048 -4.832695 3.930860 C -1.705162 -3.433253 1.963384 C -0.582666 -2.670773 3.949597 C -0.922473 -3.858894 4.599037 C -2.042830 -4.623247 2.612592 H -2.016954 -3.338210 0.927582 H 0.007544 -1.944731 4.508753 H -0.607883 -4.035367 5.627643 H -2.600454 -5.401832 2.092855 C -2.351349 0.270743 3.334123 H -1.992171 0.241152 4.367766 H -3.079972 -0.537002 3.203160 H -2.878288 1.220187 3.191133 Cl 0.681524 1.722118 -2.303056 C -2.713581 -5.640091 -2.427759 C -3.074129 -5.666403 -3.928097 H -2.171387 -5.688230 -4.550032 H -3.659008 -4.790393 -4.229120 H -3.671383 -6.551766 -4.175532 C -4.011126 -5.570833 -1.591709 H -3.786397 -5.510817 -0.520165 H -4.633189 -6.459093 -1.752936 H -4.626274 -4.701596 -1.848025 C -2.036151 -6.988531 -2.093255 H -1.755056 -7.046408 -1.035152 H -1.135721 -7.150325 -2.697129 H -2.710046 -7.829826 -2.295408 C 3.134599 6.563722 1.303265 C 2.984395 7.351643 -0.016330 H 3.375013 8.370961 0.085292 H 1.938861 7.440263 -0.330824 H 3.532698 6.863810 -0.830973 C 2.311249 7.259958 2.408972 H 2.679632 8.275479 2.595939 H 2.370121 6.704618 3.352576 H 1.251800 7.348656 2.145268 C 4.620415 6.654358 1.719893 H 4.931051 7.698081 1.850114 H 5.280027 6.216086 0.961879 H 4.804553 6.143410 2.672152 H -1.912126 -5.763084 4.436893 Table 2, Entry a Co -0.296700 0.381491 -0.672456 N -1.281967 2.151332 -0.391067 N -1.973182 -0.019567 -1.788886 C -0.621859 3.185630 -0.000814 H -1.200398 4.113556 0.139622 C -2.241365 -1.239223 -2.102892 H -3.177090 -1.413424 -2.659065
92
C 0.828959 3.277606 0.227332 C 3.525452 3.772473 0.673412 C 1.716126 2.197369 0.318764 C 1.301817 4.593184 0.363101 C 2.655922 4.870434 0.585741 C 3.098583 2.428140 0.551350 H 0.611010 5.433734 0.294184 H 4.578277 3.976641 0.848728 C -1.438924 -2.428447 -1.782922 C -0.098750 -4.833927 -1.459571 C -2.115045 -3.646644 -1.949649 C -0.089786 -2.411591 -1.412336 C 0.630579 -3.630294 -1.301287 C -1.468312 -4.874313 -1.766208 H -3.168199 -3.654331 -2.229995 H 0.421056 -5.782146 -1.352587 C -2.723998 2.053578 -0.766623 H -3.212882 1.520611 0.057500 C -2.770048 1.215452 -2.063887 H -2.247021 1.731383 -2.880717 O 1.309609 0.891183 0.272163 O 0.607373 -1.255169 -1.200083 C -4.216979 0.954470 -2.472471 H -4.260737 0.395819 -3.414927 H -4.731164 0.348817 -1.714867 C -3.418558 3.395524 -0.977252 H -2.890060 3.993151 -1.731241 H -3.425508 3.980082 -0.049602 C -4.866319 3.178491 -1.425850 H -5.333537 4.146366 -1.640040 H -5.434424 2.726488 -0.603115 C -4.964987 2.277778 -2.656496 H -6.018510 2.075942 -2.880839 H -4.551369 2.807666 -3.523672 C 4.140467 1.278895 0.671386 C 2.168243 -3.690583 -1.065583 C 3.809084 0.380471 1.882552 H 4.563043 -0.405536 2.009274 H 2.846264 -0.124654 1.791233 H 3.780627 0.966755 2.808755 C 4.167606 0.446968 -0.628910 H 4.920982 -0.347860 -0.575079 H 4.409667 1.077595 -1.492702 H 3.215404 -0.039706 -0.843681 C 2.549934 -3.039968 0.277722 H 1.998678 -3.494952 1.108255 H 2.351670 -1.968400 0.293050 H 3.620194 -3.156620 0.486170 C 2.902621 -2.978714 -2.224945 H 2.647250 -3.434800 -3.188946 H 3.990328 -3.045312 -2.103270 H 2.660298 -1.915445 -2.296426 C 2.751057 -5.128615 -1.017018 H 2.574394 -5.670529 -1.953569 H 2.323569 -5.710730 -0.192145 H 3.837119 -5.110391 -0.862825 C 5.600996 1.757827 0.890894
H 6.289888 0.906612 0.958008 H 5.706676 2.324231 1.823642 H 5.951118 2.384733 0.062373 N -1.172992 -0.409042 0.932125 C -0.352535 -1.155534 1.793245 C -0.957015 0.192015 2.186865 H 0.723250 -1.170378 1.677475 H -0.229619 0.995600 2.269782 C -0.835447 -2.442014 2.384501 H -1.926360 -2.494810 2.453471 H -0.419665 -2.573635 3.388202 H -0.502421 -3.282658 1.768536 C -2.053908 0.267952 3.228207 C -4.020846 0.469446 5.256877 C -3.426607 0.268699 2.923404 C -1.704594 0.370536 4.588098 C -2.671951 0.470076 5.591126 C -4.399901 0.366355 3.923098 H -3.764838 0.166919 1.899532 H -0.655969 0.366992 4.883265 H -2.371923 0.541528 6.634943 H -5.457337 0.350174 3.668056 H -4.775118 0.538739 6.038330 H -2.067824 -0.863766 0.769938 C -2.246586 -6.197539 -1.932584 C -1.404988 -7.465529 -1.662168 H -1.002896 -7.472619 -0.642322 H -0.565933 -7.551111 -2.362438 H -2.010127 -8.372997 -1.776616 C -3.435331 -6.226665 -0.946478 H -3.091077 -6.116303 0.088729 H -3.984060 -7.173210 -1.016567 H -4.156711 -5.425498 -1.140365 C -2.780822 -6.303484 -3.377168 H -1.961813 -6.256366 -4.104674 H -3.482576 -5.498120 -3.620051 H -3.312162 -7.249553 -3.533685 C 3.139687 6.330388 0.726724 C 4.659916 6.473794 0.966905 H 4.947612 7.528179 1.058018 H 5.241112 6.053080 0.138055 H 4.971394 5.975324 1.892260 C 2.809014 7.111622 -0.563785 H 3.173026 8.144086 -0.505093 H 1.731447 7.163497 -0.753734 H 3.275097 6.642682 -1.438505 C 2.426479 6.998002 1.922773 H 2.776773 8.026675 2.067859 H 2.615485 6.446971 2.851705 H 1.340894 7.046912 1.784727 Cl 0.546498 1.248002 -2.459293 Table 2, Entry b Co -0.436059 0.661941 -0.514526 N -1.431927 2.420905 -0.217176 N -2.100296 0.281177 -1.665427 C -0.773490 3.463011 0.155265
93
H -1.354619 4.390126 0.290471 C -2.323563 -0.917167 -2.076620 H -3.238105 -1.069953 -2.672833 C 0.677838 3.561583 0.377683 C 3.370662 4.062571 0.834841 C 1.563694 2.482490 0.494109 C 1.150313 4.879260 0.490300 C 2.503240 5.159539 0.716262 C 2.943536 2.716239 0.737231 H 0.460536 5.718598 0.400434 H 4.422227 4.269269 1.014878 C -1.504286 -2.108145 -1.823016 C -0.153784 -4.518240 -1.586526 C -2.144694 -3.318976 -2.134992 C -0.183740 -2.102665 -1.361583 C 0.541786 -3.322228 -1.282104 C -1.493826 -4.550101 -2.000755 H -3.175753 -3.318190 -2.488725 H 0.371354 -5.466331 -1.509355 C -2.878834 2.303552 -0.561900 H -3.338237 1.732922 0.256548 C -2.929481 1.507865 -1.884112 H -2.432751 2.061730 -2.692588 O 1.155229 1.176322 0.459861 O 0.488169 -0.961339 -1.026507 C -4.378700 1.227158 -2.273312 H -4.430089 0.703842 -3.235324 H -4.861705 0.580629 -1.529134 C -3.607185 3.635192 -0.713391 H -3.110870 4.268182 -1.460402 H -3.603909 4.189882 0.232521 C -5.059208 3.398056 -1.136272 H -5.554086 4.360721 -1.307481 H -5.597621 2.904989 -0.317230 C -5.163125 2.536856 -2.394342 H -6.216128 2.316138 -2.602835 H -4.782305 3.106156 -3.251536 C 3.982593 1.568744 0.892930 C 2.056834 -3.390475 -0.928621 C 3.627303 0.682386 2.106492 H 4.384654 -0.094990 2.263022 H 2.672678 0.165737 1.995479 H 3.568969 1.279733 3.024133 C 4.034231 0.722618 -0.396657 H 4.783553 -0.073976 -0.318609 H 4.295342 1.342415 -1.262709 H 3.084075 0.237690 -0.623531 C 2.337575 -2.783564 0.459805 H 1.703893 -3.242380 1.227011 H 2.172482 -1.706626 0.486083 H 3.382083 -2.936003 0.757155 C 2.870011 -2.642041 -2.008711 H 2.707122 -3.085072 -2.998592 H 3.944708 -2.687775 -1.796466 H 2.606403 -1.584084 -2.083964 C 2.638832 -4.829006 -0.879269 H 2.551223 -5.337589 -1.846545
H 2.139964 -5.440205 -0.117915 H 3.706774 -4.815444 -0.628319 C 5.438182 2.050384 1.136990 H 6.124795 1.200083 1.232832 H 5.523135 2.631985 2.062480 H 5.807541 2.663353 0.306405 N -1.323628 -0.142379 1.073458 C -0.516965 -0.882102 1.969092 C -1.137829 0.477414 2.312342 H 0.558493 -0.871406 1.828994 H -0.420871 1.276429 2.464676 H -2.239179 -0.556000 0.910505 C -1.028889 -2.131332 2.654337 C -1.901705 -4.473321 3.984112 C -1.764804 -3.123434 1.986138 C -0.732844 -2.362085 4.010770 C -1.166172 -3.514526 4.671201 C -2.199633 -4.280040 2.639807 H -2.005752 -3.010217 0.936667 H -0.148898 -1.634499 4.571889 H -0.923783 -3.667024 5.720943 H -2.765620 -5.036026 2.100713 H -2.235459 -5.373723 4.495577 C -2.288768 0.620865 3.256536 H -1.937713 0.573689 4.291882 H -3.052779 -0.149740 3.113521 H -2.766634 1.594298 3.106676 Cl 0.423568 1.544767 -2.285672 C -2.235507 -5.864544 -2.325295 C -2.666466 -5.861327 -3.807741 H -1.799999 -5.746339 -4.469760 H -3.363949 -5.047822 -4.035286 H -3.168842 -6.798271 -4.075365 C -3.488928 -5.986053 -1.430673 H -3.218580 -5.958757 -0.368585 H -4.017077 -6.928709 -1.616129 H -4.207149 -5.178289 -1.608055 C -1.392997 -7.140123 -2.096824 H -1.065058 -7.225336 -1.054196 H -0.504471 -7.158283 -2.738624 H -1.972157 -8.042469 -2.327307 C 2.988053 6.621586 0.829596 C 2.665075 7.376412 -0.478488 H 3.030164 8.409420 -0.439254 H 1.588578 7.425739 -0.675055 H 3.135033 6.888921 -1.340907 C 2.269325 7.314458 2.007804 H 2.619863 8.345613 2.133353 H 2.452975 6.782646 2.948931 H 1.184516 7.361368 1.863101 C 4.507191 6.768318 1.074595 H 4.795807 7.824082 1.144332 H 5.092115 6.328925 0.258152 H 4.813193 6.289762 2.012207 Table 3, Entry a Co 0.213765 0.132598 -0.581231
94
N -0.726060 1.902323 -0.315343 N -1.460336 -0.290061 -1.634663 C -0.071477 2.916649 0.133935 H -0.653453 3.833318 0.332650 C -1.686759 -1.500035 -2.014213 H -2.599847 -1.672512 -2.609969 C 1.375763 3.011491 0.354578 C 4.081762 3.486050 0.777296 C 2.263476 1.928528 0.411339 C 1.844882 4.323219 0.514011 C 3.195868 4.567106 0.736291 C 3.652608 2.149099 0.631116 H 1.170443 5.178993 0.466665 H 5.133092 3.724456 0.937389 C -0.875869 -2.686200 -1.720969 C 0.499091 -5.080719 -1.439464 C -1.537305 -3.904107 -1.928363 C 0.470444 -2.662175 -1.334702 C 1.208748 -3.875636 -1.241836 C -0.863260 -5.107701 -1.755048 H -2.584764 -3.938863 -2.229071 H 0.999893 -6.045913 -1.367229 C -2.174995 1.882503 -0.698710 H -2.683031 1.487906 0.188725 C -2.335100 0.900506 -1.895539 H -1.919413 1.338596 -2.812282 O 1.844491 0.627302 0.350139 O 1.148709 -1.498406 -1.100766 C 4.692484 0.998215 0.715524 C 2.742651 -3.924905 -0.993352 C 4.380107 0.085838 1.920874 H 5.126026 -0.712147 2.015946 H 3.407102 -0.402617 1.847994 H 4.383981 0.658076 2.856311 C 4.694780 0.184774 -0.595859 H 5.443739 -0.615379 -0.564728 H 4.927352 0.825735 -1.454650 H 3.735919 -0.291789 -0.802189 C 3.108938 -3.277056 0.355004 H 2.550806 -3.735578 1.179058 H 2.906841 -2.206543 0.369968 H 4.177499 -3.390055 0.573844 C 3.478071 -3.203549 -2.145283 H 3.244806 -3.668360 -3.110766 H 4.565089 -3.247882 -2.008807 H 3.212872 -2.146380 -2.225244 C 3.333319 -5.359486 -0.944219 H 3.176293 -5.896559 -1.886994 H 2.894201 -5.949486 -0.131154 H 4.416520 -5.335637 -0.771877 C 6.156463 1.474518 0.914891 H 6.846591 0.622699 0.956264 H 6.279425 2.027204 1.853700 H 6.490227 2.114785 0.089865 N -0.641677 -0.644821 1.044176 C 0.187395 -1.410623 1.879749 C -0.384636 -0.055614 2.297428
H 1.260114 -1.441057 1.740828 H 0.356973 0.735382 2.371333 C -0.302168 -2.695603 2.468805 H -1.391241 -2.727530 2.572142 H 0.142763 -2.849880 3.456646 H -0.005358 -3.533451 1.830749 C -1.454932 0.027051 3.364395 C -3.375714 0.232347 5.434918 C -2.826101 0.155695 3.083890 C -1.081677 0.007191 4.721283 C -2.026736 0.107299 5.745170 C -3.777448 0.255168 4.103954 H -3.179620 0.159488 2.061575 H -0.032546 -0.093535 4.996797 H -1.709587 0.083223 6.786122 H -4.835741 0.341506 3.867345 H -4.112737 0.304304 6.232480 H -1.548975 -1.083277 0.903928 C -1.558515 -6.419617 -1.992583 C 3.712151 5.972842 0.873373 Cl 1.027149 0.987923 -2.386177 C -3.795065 0.537267 -2.126095 C -6.483419 -0.109126 -2.619801 C -4.395329 0.856047 -3.356426 C -4.571686 -0.107490 -1.143519 C -5.906249 -0.428113 -1.394491 C -5.730516 0.532780 -3.598244 H -3.849781 1.368962 -4.148630 H -4.173287 -0.382135 -0.169057 H -6.509347 -0.925212 -0.635203 H -6.194184 0.787533 -4.550955 H -7.527308 -0.354665 -2.812147 C -2.732213 3.261229 -1.021671 C -3.791669 5.808594 -1.546110 C -3.738907 3.802157 -0.202807 C -2.267962 4.021466 -2.112990 C -2.797410 5.287016 -2.368327 C -4.262403 5.067804 -0.466343 H -4.145378 3.255768 0.648453 H -1.491991 3.666011 -2.789047 H -2.442818 5.875462 -3.214203 H -5.047476 5.481056 0.166384 H -4.207961 6.794328 -1.751090 H -1.434949 -6.724325 -3.036301 H -1.149666 -7.200203 -1.342436 H -2.628021 -6.340561 -1.770968 H 4.559661 6.010495 1.565816 H 4.032404 6.349379 -0.102908 H 2.938323 6.637315 1.271932 Table 3, Entry b Co 0.091201 0.456162 -0.490694 N -0.834168 2.229539 -0.229717 N -1.554182 0.053973 -1.570146 C -0.162937 3.255305 0.165708 H -0.732344 4.183556 0.344886 C -1.721945 -1.115013 -2.080527
95
H -2.616142 -1.250341 -2.714388 C 1.287114 3.341387 0.367201 C 3.992283 3.791035 0.808830 C 2.152512 2.246758 0.498862 C 1.778126 4.651862 0.450644 C 3.134194 4.883986 0.651909 C 3.539202 2.455199 0.743005 H 1.117793 5.514791 0.358110 H 5.042045 4.019667 0.992090 C -0.883055 -2.299589 -1.884584 C 0.506294 -4.697930 -1.722277 C -1.489766 -3.496407 -2.295012 C 0.418726 -2.300330 -1.366233 C 1.162540 -3.514988 -1.314607 C -0.810906 -4.704181 -2.188502 H -2.502291 -3.512107 -2.699922 H 1.017212 -5.660150 -1.699214 C -2.298719 2.185577 -0.536416 H -2.751784 1.773013 0.374366 C -2.497771 1.211535 -1.732680 H -2.179974 1.680669 -2.672890 O 1.705979 0.952275 0.491041 O 1.056997 -1.165999 -0.947668 C 4.553231 1.294681 0.935816 C 2.657380 -3.586069 -0.891938 C 4.165074 0.435965 2.158759 H 4.905916 -0.352048 2.339269 H 3.202968 -0.065182 2.042893 H 4.104698 1.049868 3.065280 C 4.606048 0.428830 -0.338580 H 5.324917 -0.391953 -0.231765 H 4.907533 1.025601 -1.207722 H 3.643062 -0.022212 -0.578963 C 2.876859 -3.000575 0.516772 H 2.207201 -3.467847 1.247484 H 2.715733 -1.923707 0.552925 H 3.906186 -3.161689 0.859158 C 3.510473 -2.822029 -1.927731 H 3.415071 -3.272872 -2.922987 H 4.572234 -2.838916 -1.655445 H 3.219057 -1.773333 -2.025854 C 3.236763 -5.025383 -0.835529 H 3.210296 -5.515477 -1.815785 H 2.691110 -5.651143 -0.119461 H 4.287547 -5.016816 -0.520257 C 6.012528 1.756848 1.193115 H 6.682874 0.897302 1.317221 H 6.092210 2.356887 2.107213 H 6.405403 2.346361 0.356394 N -0.797567 -0.317499 1.104698 C 0.001405 -1.060210 2.006525 C -0.608401 0.307230 2.339531 H 1.077949 -1.060698 1.874587 H 0.114937 1.101611 2.487336 H -1.710483 -0.739165 0.946976 C -0.531626 -2.310754 2.672715 C -1.452698 -4.657681 3.959054
C -1.208924 -3.317832 1.964942 C -0.315954 -2.530133 4.045672 C -0.774284 -3.684991 4.684672 C -1.667898 -4.476757 2.597284 H -1.381442 -3.215673 0.900461 H 0.223641 -1.792651 4.637379 H -0.594940 -3.829207 5.748222 H -2.186335 -5.244861 2.027923 H -1.804578 -5.560288 4.454360 C -1.761776 0.469609 3.277626 H -1.415328 0.430807 4.314818 H -2.531285 -0.296405 3.139285 H -2.231489 1.445085 3.115569 Cl 0.946564 1.300530 -2.281729 C -1.446682 -5.988393 -2.643283 C 3.666409 6.285577 0.768861 C -2.904315 3.552890 -0.818791 C -4.056393 6.074469 -1.269876 C -3.891556 4.056082 0.046292 C -2.509009 4.337018 -1.920608 C -3.083599 5.589798 -2.138933 C -4.460943 5.309030 -0.180553 H -4.249558 3.487498 0.904782 H -1.753551 4.010389 -2.633401 H -2.781893 6.196718 -2.992260 H -5.231479 5.692253 0.487972 H -4.508622 7.049918 -1.445991 C -3.952493 0.775857 -1.845304 C -6.635037 -0.007291 -2.117589 C -4.681866 1.106666 -3.000232 C -4.596632 0.051366 -0.823026 C -5.929054 -0.337306 -0.964632 C -6.013984 0.714789 -3.132286 H -4.241852 1.680988 -3.815539 H -4.095299 -0.230163 0.101812 H -6.430060 -0.895520 -0.174157 H -6.578752 0.978093 -4.026280 H -7.677360 -0.306157 -2.223538 H -1.094625 -6.831965 -2.040264 H -2.535555 -5.945112 -2.535161 H -1.202588 -6.174656 -3.693599 H 4.683999 6.350234 0.369490 H 3.675081 6.595041 1.818443 H 3.049171 6.987473 0.198288 Table 3, Entry c Co -0.104928 0.280078 -0.615657 N -1.177847 2.085106 -0.485288 N -1.697051 -0.152349 -1.921454 C -0.578960 3.112375 0.008041 H -1.182334 4.031198 0.092054 C -1.909197 -1.385231 -2.227542 H -2.781363 -1.590053 -2.869758 C 0.833321 3.215706 0.412310 C 3.454755 3.771746 1.154664 C 1.738208 2.156770 0.572934 C 1.252824 4.538887 0.635315
96
C 2.565773 4.846726 1.010709 C 3.084763 2.420993 0.947514 H 0.550659 5.364197 0.514070 H 4.477043 3.999506 1.444011 C -1.112824 -2.550643 -1.811393 C 0.248145 -4.927817 -1.368717 C -1.748362 -3.784659 -2.019247 C 0.201892 -2.505525 -1.330870 C 0.939448 -3.708645 -1.167700 C -1.094356 -4.997768 -1.773438 H -2.775151 -3.816773 -2.383402 H 0.778215 -5.864342 -1.218082 C -2.578508 2.000666 -1.067864 C -2.476902 1.081377 -2.340716 O 1.386753 0.837922 0.464654 O 0.857239 -1.340926 -1.044924 C -3.908193 0.771359 -2.823731 H -3.891438 0.142354 -3.723286 H -4.463045 0.196898 -2.071857 C -3.146159 3.364526 -1.513637 H -2.464766 3.868384 -2.209958 H -3.252068 4.045332 -0.659154 C -4.532156 3.221179 -2.173365 H -4.783939 4.159889 -2.682319 H -5.290658 3.114416 -1.388527 C -4.691719 2.055514 -3.160543 H -5.756490 1.809059 -3.256206 H -4.393507 2.404331 -4.156495 C 4.150588 1.300807 1.130647 C 2.462556 -3.734201 -0.840925 C 3.753801 0.373651 2.298641 H 4.518656 -0.392468 2.472728 H 2.816896 -0.156138 2.122795 H 3.634841 0.942833 3.228268 C 4.308232 0.490114 -0.174565 H 5.091971 -0.270443 -0.076172 H 4.581657 1.143880 -1.011322 H 3.398809 -0.038761 -0.462441 C 2.753623 -3.095267 0.530157 H 2.181626 -3.586356 1.324715 H 2.515620 -2.031967 0.554793 H 3.816148 -3.177860 0.788758 C 3.246254 -2.986539 -1.945123 H 3.050410 -3.425916 -2.930550 H 4.326923 -3.038942 -1.766661 H 2.991965 -1.925333 -2.006856 C 3.077133 -5.158672 -0.781045 H 2.962035 -5.690938 -1.732606 H 2.622277 -5.762644 0.012876 H 4.152909 -5.117068 -0.569812 C 5.574324 1.819994 1.469988 H 6.284589 0.989651 1.568663 H 5.592646 2.364114 2.421604 H 5.962798 2.479404 0.684920 N -1.077800 -0.568775 0.938939 C -0.263366 -1.264785 1.856084 C -0.978174 0.035467 2.205283
H 0.815661 -1.204744 1.814828 H -0.313270 0.889305 2.307365 C -0.685860 -2.582745 2.422718 H -1.758549 -2.769214 2.324162 H -0.418979 -2.640490 3.482455 H -0.169544 -3.394072 1.901527 C -2.128430 0.062620 3.197751 C -4.200714 0.234510 5.133322 C -3.386106 -0.533356 2.991649 C -1.950764 0.738767 4.422006 C -2.968540 0.827561 5.376256 C -4.409515 -0.449981 3.942287 H -3.589034 -1.101489 2.089811 H -0.993164 1.202347 4.655625 H -2.794440 1.349159 6.315428 H -5.367088 -0.934013 3.761778 H -4.990836 0.291261 5.879299 H -1.895845 -1.116795 0.694402 C -1.832201 -6.337619 -1.984881 C -0.992476 -7.585746 -1.629525 H -0.672028 -7.570819 -0.581236 H -0.099425 -7.665672 -2.260218 H -1.570637 -8.505892 -1.777343 C -3.096833 -6.378424 -1.098505 H -2.840416 -6.248641 -0.040321 H -3.620044 -7.336505 -1.200012 H -3.815120 -5.594375 -1.361476 C -2.244594 -6.470579 -3.466582 H -1.369847 -6.416743 -4.125505 H -2.938152 -5.681238 -3.776431 H -2.744572 -7.428190 -3.653279 C 2.986251 6.314093 1.245631 C 4.465295 6.491090 1.658584 H 4.708183 7.549315 1.813388 H 5.147720 6.114991 0.887466 H 4.687533 5.970183 2.597226 C 2.777207 7.125635 -0.051528 H 3.100481 8.165387 0.076273 H 1.726341 7.153608 -0.359482 H 3.351844 6.697098 -0.881240 C 2.124923 6.924889 2.372657 H 2.426101 7.957445 2.584915 H 2.225917 6.350278 3.301042 H 1.060418 6.949497 2.115479 Cl 0.999665 1.102375 -2.274255 C -3.484901 1.455080 0.061954 H -3.325632 0.393983 0.240005 H -4.551632 1.541252 -0.160821 H -3.318676 1.993527 1.002493 C -1.692114 1.700678 -3.531626 H -0.799838 2.242730 -3.214847 H -2.275249 2.437042 -4.090914 H -1.385538 0.933034 -4.252683 Table 3, Entry d Co -0.291962 0.516254 -0.506144 N -1.346834 2.340414 -0.424725
97
N -1.956102 0.031883 -1.702557 C -0.707899 3.392478 -0.047102 H -1.296147 4.323195 0.007948 C -2.166414 -1.206778 -1.980718 H -3.061112 -1.427015 -2.585723 C 0.728114 3.506533 0.257893 C 3.394674 4.079639 0.798255 C 1.630469 2.450056 0.444529 C 1.173524 4.836759 0.351545 C 2.509860 5.153325 0.622554 C 2.999240 2.722463 0.719584 H 0.473710 5.660548 0.208667 H 4.434592 4.313937 1.008835 C -1.346340 -2.359660 -1.585153 C 0.019132 -4.731447 -1.130709 C -1.979489 -3.598535 -1.781997 C -0.026248 -2.305321 -1.121386 C 0.709257 -3.508814 -0.942223 C -1.322870 -4.808465 -1.532088 H -3.009206 -3.636890 -2.137651 H 0.550315 -5.665475 -0.969580 C -2.781121 2.232411 -0.913246 C -2.758231 1.245825 -2.136502 O 1.259567 1.132470 0.455161 O 0.638747 -1.138967 -0.867098 C -4.216595 0.917955 -2.516283 H -4.256050 0.243923 -3.381762 H -4.725459 0.384952 -1.703859 C -3.369890 3.573975 -1.400918 H -2.731358 4.033186 -2.165347 H -3.419805 4.303049 -0.581790 C -4.794674 3.403072 -1.963805 H -5.075943 4.314013 -2.506609 H -5.502588 3.342918 -1.128342 C -5.016753 2.186272 -2.873959 H -6.085876 1.940792 -2.891393 H -4.778485 2.478757 -3.903685 C 4.062427 1.604422 0.929950 C 2.230490 -3.535810 -0.606379 C 3.722886 0.775121 2.186308 H 4.490303 0.015847 2.378253 H 2.774174 0.243895 2.102400 H 3.658858 1.415791 3.073844 C 4.137488 0.693403 -0.314612 H 4.918599 -0.067872 -0.202008 H 4.367576 1.276451 -1.214275 H 3.207943 0.156439 -0.506774 C 2.524321 -2.836394 0.734396 H 1.909103 -3.251802 1.539999 H 2.346289 -1.762043 0.691658 H 3.575146 -2.956840 1.024148 C 3.022086 -2.849538 -1.743265 H 2.840682 -3.347900 -2.703112 H 4.100780 -2.883223 -1.549527 H 2.758104 -1.796738 -1.872047 C 2.830668 -4.961681 -0.474171 H 2.726385 -5.535001 -1.402835
H 2.357353 -5.525282 0.338487 H 3.903739 -4.920287 -0.249495 C 5.508191 2.127490 1.148498 H 6.214344 1.297049 1.272591 H 5.585408 2.743572 2.052078 H 5.858803 2.718090 0.293906 N -1.166219 -0.215654 1.149756 C -0.306464 -0.853611 2.080341 C -1.005495 0.482177 2.348298 H 0.764020 -0.787523 1.928398 H -0.343386 1.335627 2.436641 H -2.024634 -0.738838 1.003374 C -0.728789 -2.086297 2.855357 C -1.417117 -4.386701 4.357415 C -1.481567 -3.131109 2.294801 C -0.322165 -2.242661 4.194133 C -0.663612 -3.374099 4.939335 C -1.825104 -4.267219 3.033682 H -1.810443 -3.076976 1.264537 H 0.277074 -1.470598 4.673920 H -0.336736 -3.467217 5.972939 H -2.407429 -5.063847 2.576903 H -1.680862 -5.270296 4.934721 C -2.125938 0.587973 3.333509 H -1.742586 0.505231 4.355204 H -2.891194 -0.180353 3.184890 H -2.610166 1.564631 3.242636 Cl 0.716789 1.218788 -2.277153 C -2.058247 -6.151241 -1.730196 C -2.470432 -6.298160 -3.210530 H -1.595739 -6.249635 -3.869939 H -3.164502 -5.512036 -3.527425 H -2.969626 -7.257834 -3.388487 C -3.322875 -6.187145 -0.843600 H -3.066608 -6.049812 0.213358 H -3.844744 -7.146673 -0.938093 H -4.042427 -5.406130 -1.111843 C -1.216085 -7.394250 -1.362995 H -0.895563 -7.368408 -0.314899 H -0.322977 -7.478631 -1.993012 H -1.792503 -8.316884 -1.501784 C 2.958892 6.628047 0.715957 C 2.678781 7.339565 -0.625781 H 3.019929 8.381131 -0.599639 H 1.611311 7.359358 -0.870829 H 3.196888 6.839375 -1.452611 C 2.174691 7.337215 1.841653 H 2.498712 8.378559 1.953662 H 2.326805 6.835012 2.804422 H 1.096689 7.357515 1.648215 C 4.462262 6.814482 1.023454 H 4.725058 7.877790 1.079241 H 5.092084 6.368943 0.244610 H 4.736425 6.365334 1.985162 C -3.623970 1.765619 0.300067 H -3.429459 0.733329 0.582430 H -4.700756 1.803504 0.114702
98
H -3.437899 2.400051 1.174342 C -2.045023 1.796556 -3.404682 H -1.126645 2.338220 -3.172845 H -2.654852 2.513957 -3.960214 H -1.795494 0.990983 -4.106149 Table 3, Entry e Co -0.241645 0.371520 -0.708547 N -1.287848 2.121796 -0.558967 N -1.788213 -0.085708 -1.981009 C -0.692386 3.177822 -0.125172 H -1.301367 4.094765 -0.062872 C -1.995675 -1.315814 -2.300085 H -2.866902 -1.520687 -2.943762 C 0.725252 3.307010 0.247416 C 3.350718 3.870886 0.957104 C 1.621418 2.249152 0.447438 C 1.153352 4.635101 0.407583 C 2.471306 4.946947 0.762221 C 2.967582 2.515365 0.815516 H 0.455569 5.458478 0.253676 H 4.375584 4.102094 1.234824 C -1.201029 -2.480080 -1.883728 C 0.158899 -4.846712 -1.398088 C -1.828752 -3.716853 -2.096421 C 0.105179 -2.424536 -1.385078 C 0.840818 -3.623220 -1.188788 C -1.173680 -4.925412 -1.833253 H -2.849248 -3.754698 -2.477219 H 0.688629 -5.780217 -1.228414 C -2.682196 1.984993 -1.076874 H -3.240154 1.453220 -0.296736 C -2.579205 1.126134 -2.357181 H -1.987428 1.641168 -3.126242 O 1.250316 0.933335 0.381998 O 0.750075 -1.248530 -1.121098 C -3.971555 0.825484 -2.904502 H -3.907951 0.251523 -3.836572 H -4.546454 0.219798 -2.191904 C -3.380781 3.307044 -1.379684 H -2.791942 3.905201 -2.087104 H -3.493877 3.905351 -0.467798 C -4.770859 3.049645 -1.967735 H -5.234801 4.003034 -2.244790 H -5.409248 2.597233 -1.198500 C -4.725398 2.128160 -3.186072 H -5.746308 1.898593 -3.511680 H -4.237811 2.654139 -4.016409 C 4.016590 1.392577 1.059843 C 2.350323 -3.642131 -0.808161 C 3.581820 0.501632 2.243585 H 4.336600 -0.263792 2.459839 H 2.645909 -0.028539 2.060559 H 3.443407 1.098743 3.152806 C 4.196272 0.545620 -0.218418 H 4.955844 -0.231986 -0.074938 H 4.514460 1.170775 -1.061257
H 3.281632 0.036169 -0.524392 C 2.586853 -2.969521 0.557447 H 1.969361 -3.429429 1.337130 H 2.363450 -1.902932 0.540618 H 3.634711 -3.058233 0.868308 C 3.173827 -2.922550 -1.901024 H 3.021606 -3.393285 -2.879674 H 4.246449 -2.961148 -1.676643 H 2.914255 -1.866218 -2.006740 C 2.960953 -5.064349 -0.688115 H 2.886079 -5.619559 -1.630531 H 2.472449 -5.649172 0.100150 H 4.027004 -5.017047 -0.433280 C 5.435593 1.908416 1.421812 H 6.132232 1.074506 1.573236 H 5.431315 2.489647 2.351412 H 5.856195 2.532122 0.624236 N -1.257629 -0.420369 0.822451 C -0.501170 -1.151538 1.752818 C -1.160799 0.186662 2.088976 H 0.580736 -1.146307 1.732333 H -0.460885 1.006461 2.228932 C -1.010340 -2.447310 2.300490 H -2.101976 -2.520043 2.273244 H -0.681976 -2.572126 3.336933 H -0.608992 -3.281359 1.717244 C -2.341112 0.234646 3.037914 C -4.472469 0.372804 4.895064 C -3.682376 0.247700 2.615485 C -2.109085 0.293498 4.426347 C -3.159451 0.361655 5.347754 C -4.738993 0.314197 3.531396 H -3.929821 0.182490 1.562710 H -1.088885 0.280496 4.809319 H -2.945015 0.401785 6.413830 H -5.768642 0.311141 3.180656 H -2.127223 -0.889172 0.581431 C -1.900530 -6.269864 -2.053726 C -1.059375 -7.512666 -1.683450 H -0.757748 -7.495942 -0.629620 H -0.154746 -7.586711 -2.298166 H -1.629035 -8.436435 -1.841339 C -3.178442 -6.315942 -1.186997 H -2.939120 -6.183321 -0.125167 H -3.695086 -7.276852 -1.295153 H -3.896453 -5.535848 -1.462242 C -2.289196 -6.408021 -3.541427 H -1.404709 -6.349966 -4.186851 H -2.982823 -5.623670 -3.863515 H -2.780327 -7.369041 -3.734023 C 2.906787 6.419728 0.926018 C 4.390930 6.601858 1.317802 H 4.645114 7.663875 1.419339 H 5.062979 6.182107 0.560214 H 4.616424 6.124874 2.278745 C 2.693645 7.173061 -0.405194 H 3.027543 8.214441 -0.327929
99
H 1.640394 7.197077 -0.705209 H 3.256948 6.701539 -1.219215 C 2.060534 7.089130 2.030861 H 2.372076 8.127714 2.192755 H 2.164931 6.557004 2.983864 H 0.994052 7.110905 1.781703 Cl 0.753928 1.233590 -2.417313 Cl -5.769765 0.459222 6.016604 Table 3, Entry f Co -0.434242 0.667883 -0.520927 N -1.431213 2.427718 -0.223011 N -2.096603 0.289802 -1.677217 C -0.773294 3.469303 0.151925 H -1.354539 4.396426 0.286767 C -2.319607 -0.908320 -2.089464 H -3.231842 -1.060435 -2.689439 C 0.677673 3.567444 0.376982 C 3.370102 4.068291 0.836677 C 1.563754 2.488327 0.492134 C 1.149718 4.885014 0.492598 C 2.502374 5.165216 0.720165 C 2.943529 2.722024 0.735852 H 0.459925 5.724475 0.403687 H 4.421546 4.275087 1.017457 C -1.503052 -2.100202 -1.830076 C -0.157979 -4.512033 -1.579721 C -2.146441 -3.311211 -2.134788 C -0.182202 -2.095388 -1.368808 C 0.540926 -3.315893 -1.283628 C -1.498586 -4.543106 -1.992532 H -3.177174 -3.310045 -2.489681 H 0.365192 -5.461009 -1.498675 C -2.877038 2.311391 -0.573486 H -3.339320 1.739274 0.242340 C -2.923433 1.517924 -1.897425 H -2.422989 2.072509 -2.703084 O 1.155625 1.182057 0.456209 O 0.491638 -0.953319 -1.039549 C -4.371366 1.239021 -2.292601 H -4.419408 0.717373 -3.255698 H -4.857682 0.591528 -1.551419 C -3.604303 3.643600 -0.725094 H -3.104930 4.277819 -1.469020 H -3.604272 4.196448 0.221904 C -5.054826 3.408020 -1.153919 H -5.548596 4.371274 -1.325016 H -5.596561 2.913527 -0.337934 C -5.154379 2.549484 -2.414164 H -6.206705 2.329916 -2.627236 H -4.769785 3.120239 -3.268699 C 3.983358 1.574787 0.888437 C 2.056803 -3.385261 -0.933816 C 3.629790 0.686417 2.100972 H 4.387345 -0.091229 2.255142 H 2.674982 0.170067 1.990379 H 3.572716 1.282211 3.019702
C 4.034036 0.730689 -0.402577 H 4.784113 -0.065409 -0.326709 H 4.293599 1.352074 -1.267957 H 3.084069 0.245231 -0.629134 C 2.340976 -2.776084 0.452833 H 1.710337 -3.234768 1.222611 H 2.174127 -1.699398 0.478086 H 3.386603 -2.926711 0.747138 C 2.868854 -2.639756 -2.016832 H 2.701746 -3.082933 -3.005937 H 3.944056 -2.688429 -1.807778 H 2.608374 -1.581008 -2.091804 C 2.637138 -4.824395 -0.883208 H 2.545402 -5.334995 -1.849038 H 2.140232 -5.433280 -0.118720 H 3.705934 -4.811617 -0.635880 C 5.439037 2.056655 1.131574 H 6.126197 1.206500 1.224763 H 5.524969 2.636341 2.058174 H 5.806958 2.671554 0.301776 N -1.322783 -0.146615 1.068501 C -0.511895 -0.880486 1.964538 C -1.141350 0.475431 2.306987 H 0.563488 -0.862842 1.823991 H -0.429968 1.279756 2.457919 H -2.237583 -0.560589 0.902905 C -1.016153 -2.134419 2.648500 C -1.871640 -4.484047 3.970729 C -1.751058 -3.126848 1.978536 C -0.713182 -2.369422 4.003670 C -1.138391 -3.527882 4.662588 C -2.178436 -4.289432 2.628886 H -1.997791 -3.009551 0.930470 H -0.130255 -1.640920 4.565491 H -0.889372 -3.678985 5.710746 H -2.744098 -5.041794 2.084776 C -2.293071 0.612041 3.251157 H -1.941557 0.567141 4.286452 H -3.052105 -0.163524 3.108435 H -2.777092 1.582387 3.101097 Cl 0.425298 1.557046 -2.288827 C -2.243314 -5.857880 -2.309568 C -2.668469 -5.864453 -3.793614 H -1.799035 -5.757698 -4.453117 H -3.361972 -5.050047 -4.029983 H -3.173259 -6.801567 -4.056031 C -3.500630 -5.968965 -1.419008 H -3.234377 -5.934516 -0.356143 H -4.030784 -6.911479 -1.599418 H -4.215909 -5.160617 -1.605282 C -1.405698 -7.134214 -2.067741 H -1.080532 -7.211136 -1.023593 H -0.515736 -7.161225 -2.707225 H -1.987350 -8.036606 -2.291673 C 2.986693 6.627209 0.836876 C 2.664975 7.384443 -0.470119 H 3.029703 8.417485 -0.428485
100
H 1.588686 7.433806 -0.667816 H 3.136065 6.898752 -1.332936 C 2.266467 7.317635 2.015613 H 2.616640 8.348619 2.143571 H 2.449159 6.784029 2.955910 H 1.181815 7.364615 1.869769 C 4.505508 6.773875 1.083903 H 4.793716 7.829573 1.156270 H 5.091496 6.336474 0.267153 H 4.810599 6.293344 2.020803 Cl -2.396855 -5.910610 4.769758 Table 3, Entry g Co -0.313663 0.554077 -0.674082 N -1.217800 2.334735 -0.239096 N -2.087728 0.265182 -1.687583 C -0.492636 3.334883 0.122999 H -1.024341 4.277847 0.331692 C -2.396615 -0.918100 -2.088228 H -3.376729 -1.030948 -2.579986 C 0.972801 3.364831 0.257366 C 3.704704 3.736115 0.598235 C 1.819098 2.248171 0.268197 C 1.505276 4.655232 0.411097 C 2.878694 4.870600 0.578199 C 3.217179 2.414832 0.456338 H 0.847349 5.524443 0.401398 H 4.771657 3.891786 0.733776 C -1.585712 -2.135984 -1.961723 C -0.255405 -4.570876 -2.015232 C -2.278265 -3.321324 -2.256576 C -0.222603 -2.173108 -1.651704 C 0.489605 -3.401008 -1.729987 C -1.636575 -4.565320 -2.263435 H -3.343700 -3.290034 -2.484880 H 0.259388 -5.526879 -2.056137 C -2.692402 2.282604 -0.467618 H -3.108212 1.710063 0.372128 C -2.884566 1.526627 -1.799942 H -2.436181 2.085624 -2.632820 O 1.363802 0.960592 0.176667 O 0.502413 -1.067388 -1.313424 C -4.370702 1.311475 -2.073093 H -4.522018 0.815610 -3.039159 H -4.816258 0.664814 -1.306014 C -3.375237 3.645425 -0.526357 H -2.915672 4.278796 -1.296164 H -3.272449 4.173384 0.429228 C -4.865664 3.476407 -0.832901 H -5.332902 4.461878 -0.940008 H -5.354787 2.983343 0.016535 C -5.108498 2.653289 -2.097474 H -6.183270 2.479044 -2.221962 H -4.777175 3.229973 -2.970150 C 4.211268 1.218993 0.507546 C 2.035796 -3.497932 -1.568811 C 3.855751 0.269857 1.674043
H 4.587858 -0.542108 1.758941 H 2.879798 -0.206369 1.561792 H 3.845887 0.809831 2.628334 C 4.188606 0.457684 -0.834553 H 4.898817 -0.377548 -0.828651 H 4.459209 1.119634 -1.665835 H 3.209350 0.036711 -1.066283 C 2.489431 -3.003361 -0.180776 H 1.981730 -3.551869 0.620058 H 2.298353 -1.941268 -0.028238 H 3.568599 -3.142260 -0.043704 C 2.722754 -2.668351 -2.677587 H 2.430251 -3.026033 -3.672157 H 3.814472 -2.740784 -2.606059 H 2.473509 -1.605284 -2.632707 C 2.603296 -4.936669 -1.704478 H 2.387176 -5.368399 -2.688796 H 2.198623 -5.604753 -0.935087 H 3.694435 -4.943868 -1.590437 C 5.691811 1.626000 0.736249 H 6.343961 0.744239 0.764675 H 5.825014 2.150806 1.689586 H 6.065538 2.269065 -0.069228 N -1.114028 -0.227304 0.925251 C -0.404114 -1.149517 1.717963 C -0.696515 0.259829 2.183350 H 0.622754 -1.388335 1.473438 H 0.190941 0.873755 2.298562 C -1.075659 -2.252150 2.539142 C -1.751391 0.424319 3.236391 C -3.812453 0.682407 5.137452 C -1.983439 1.647338 3.884300 C -2.557104 -0.669478 3.588762 C -3.592084 -0.542209 4.512445 C -3.004473 1.775002 4.829726 H -1.356651 2.510346 3.676640 H -4.213559 -1.399413 4.761024 H -3.166035 2.722246 5.341313 H -4.604218 0.778959 5.878227 H -2.102539 -0.465675 0.852759 C -2.436353 -5.852637 -2.557885 C -1.594169 -7.147592 -2.503694 H -1.138941 -7.291682 -1.516857 H -0.794069 -7.141170 -3.253044 H -2.213433 -8.030117 -2.704797 C -3.567348 -6.005938 -1.516854 H -3.163570 -6.032845 -0.497667 H -4.129822 -6.933110 -1.677742 H -4.289201 -5.183296 -1.562663 C -3.052179 -5.767706 -3.971000 H -2.275069 -5.626982 -4.731620 H -3.759530 -4.936725 -4.066407 H -3.599916 -6.684377 -4.219146 C 3.428892 6.305017 0.737527 C 4.963677 6.380012 0.905258 H 5.299159 7.418849 1.010453 H 5.485600 5.960366 0.037342
101
H 5.298985 5.842840 1.800123 C 3.068462 7.139104 -0.511315 H 3.477800 8.153694 -0.440683 H 1.986035 7.240490 -0.645397 H 3.471185 6.679421 -1.421688 C 2.802944 6.962486 1.986796 H 3.201785 7.971471 2.144247 H 3.014321 6.375615 2.888558 H 1.714816 7.058396 1.904713 Cl 0.454555 1.455256 -2.477088 O -2.407771 -1.896575 2.994450 C -1.275820 -3.494281 1.664931 H -0.330586 -3.863321 1.257727 H -1.950964 -3.273549 0.832183 H -1.746859 -4.303785 2.234519 C -0.207282 -2.632903 3.748169 H 0.770080 -3.014754 3.433534 H -0.701686 -3.394852 4.361097 H -0.028655 -1.771623 4.401219 Table 3, Entry h Co -0.269935 0.646040 -0.737553 N -1.187179 2.437351 -0.398889 N -1.975726 0.333966 -1.848182 C -0.489265 3.429345 0.032446 H -1.030001 4.375952 0.196327 C -2.299190 -0.868830 -2.174381 H -3.261917 -0.998365 -2.695560 C 0.958660 3.448456 0.294821 C 3.657288 3.801257 0.854853 C 1.797348 2.328367 0.354371 C 1.481935 4.733354 0.513689 C 2.838523 4.939376 0.793166 C 3.177951 2.485424 0.650012 H 0.830028 5.605924 0.466963 H 4.711101 3.949465 1.075048 C -1.515724 -2.088533 -1.934606 C -0.202837 -4.529841 -1.838168 C -2.218708 -3.283191 -2.151689 C -0.153953 -2.116934 -1.617280 C 0.551425 -3.350121 -1.625835 C -1.586014 -4.529826 -2.080017 H -3.282098 -3.255838 -2.388905 H 0.305725 -5.489977 -1.826061 C -2.635826 2.408443 -0.770806 H -3.145436 1.877580 0.043583 C -2.724535 1.604592 -2.086050 H -2.185593 2.118971 -2.893547 O 1.347896 1.044491 0.211325 O 0.571504 -0.994538 -1.333279 C -4.182484 1.413616 -2.492719 H -4.253663 0.877452 -3.446540 H -4.719009 0.814513 -1.745509 C -3.272835 3.783742 -0.947258 H -2.721107 4.375636 -1.689014 H -3.252051 4.346045 -0.006170 C -4.730253 3.640246 -1.394812
H -5.155130 4.632187 -1.585861 H -5.314979 3.195875 -0.579609 C -4.873351 2.771684 -2.644210 H -5.935596 2.620532 -2.867274 H -4.440952 3.302059 -3.501875 C 4.161510 1.283809 0.750179 C 2.097098 -3.445257 -1.461554 C 3.722550 0.319499 1.875007 H 4.441655 -0.499593 1.995075 H 2.752426 -0.146395 1.691255 H 3.653280 0.844622 2.835135 C 4.229797 0.542865 -0.602541 H 4.936722 -0.294146 -0.560282 H 4.559110 1.217024 -1.402262 H 3.268959 0.127273 -0.910058 C 2.542843 -2.922533 -0.082101 H 2.039504 -3.462398 0.727437 H 2.336453 -1.860423 0.050150 H 3.623188 -3.046840 0.059036 C 2.794495 -2.638973 -2.581660 H 2.486636 -2.996672 -3.571480 H 3.884863 -2.735955 -2.517502 H 2.574127 -1.569325 -2.540782 C 2.661431 -4.887516 -1.567707 H 2.433892 -5.341999 -2.539135 H 2.264511 -5.536676 -0.778349 H 3.753511 -4.893761 -1.463110 C 5.624308 1.680373 1.086539 H 6.270308 0.795457 1.143250 H 5.694056 2.187151 2.056243 H 6.053711 2.336500 0.320304 N -1.175508 -0.103461 0.824225 C -0.540605 -1.136801 1.547864 C -0.761421 0.244743 2.125737 H 0.497434 -1.385284 1.355990 H 0.125335 0.843451 2.292789 H -2.181660 -0.235087 0.729105 C -1.416807 -2.224949 2.109170 C -3.155573 -4.203887 3.118045 C -1.188877 -3.584288 1.853891 C -2.525479 -1.889347 2.907683 C -3.399950 -2.860983 3.390880 C -2.047316 -4.566048 2.356084 H -0.333598 -3.897803 1.262133 H -4.258669 -2.577017 3.993990 H -1.850808 -5.617561 2.155113 H -3.822589 -4.969534 3.509203 C -1.714659 0.326015 3.313688 Cl 0.616828 1.522414 -2.497593 C -2.393169 -5.826532 -2.306165 C -2.939944 -5.841844 -3.749456 H -2.125465 -5.775696 -4.480568 H -3.622287 -5.006549 -3.941906 H -3.495829 -6.764773 -3.951892 C -3.576077 -5.890190 -1.314270 H -3.223174 -5.847807 -0.277734 H -4.142939 -6.820901 -1.434718
102
H -4.284659 -5.067089 -1.455100 C -1.573962 -7.122456 -2.109658 H -1.151946 -7.182270 -1.099574 H -0.751099 -7.195141 -2.830230 H -2.200482 -8.011232 -2.252194 C 3.378634 6.368080 1.022813 C 3.123246 7.226133 -0.235615 H 3.528610 8.237416 -0.113461 H 2.055564 7.334755 -0.455086 H 3.597067 6.781106 -1.118631 C 2.655753 7.005982 2.229195 H 3.044039 8.009961 2.436989 H 2.791287 6.401862 3.134150 H 1.578210 7.108847 2.061065 C 4.894992 6.432733 1.315746 H 5.224006 7.467789 1.468080 H 5.484331 6.027584 0.484894 H 5.154967 5.876767 2.224088 O -2.836082 -0.582118 3.199968 C -0.972797 0.072171 4.635245 H -0.189302 0.818925 4.804062 H -0.493339 -0.912769 4.645307 H -1.666582 0.093284 5.483129 C -2.326569 1.733263 3.354540 H -1.556513 2.508606 3.428838 H -3.013334 1.838399 4.202140 H -2.916212 1.927075 2.451980 Table 3, Entry i Co -0.314933 0.585417 -0.664185 N -1.100166 2.377006 -0.066131 N -2.154474 0.449177 -1.587624 C -0.305852 3.316905 0.312224 H -0.776347 4.269762 0.606153 C -2.542382 -0.687846 -2.048942 H -3.552269 -0.721738 -2.489690 C 1.163895 3.267613 0.366424 C 3.925128 3.484872 0.578137 C 1.951306 2.114077 0.255316 C 1.768683 4.517458 0.577075 C 3.158031 4.655472 0.681894 C 3.364222 2.201323 0.374406 H 1.156602 5.415623 0.663410 H 5.004303 3.580573 0.663600 C -1.784829 -1.946149 -2.054607 C -0.577076 -4.425374 -2.363159 C -2.549543 -3.076143 -2.385939 C -0.408567 -2.064226 -1.835247 C 0.238701 -3.312286 -2.045981 C -1.969139 -4.342783 -2.520133 H -3.624021 -2.982597 -2.544263 H -0.111571 -5.396984 -2.504653 C -2.585838 2.410757 -0.213172 H -2.983166 1.804636 0.612068 C -2.889837 1.752438 -1.576097 H -2.459693 2.341645 -2.397655 O 1.427434 0.858485 0.105490
O 0.387105 -1.018574 -1.465459 C -4.397892 1.626638 -1.774758 H -4.627650 1.202344 -2.759256 H -4.832940 0.953442 -1.024664 C -3.200296 3.805289 -0.146673 H -2.752223 4.464941 -0.901020 H -3.018009 4.264337 0.832365 C -4.712058 3.727555 -0.375604 H -5.133496 4.738988 -0.393748 H -5.178093 3.204116 0.468622 C -5.066124 3.000848 -1.672594 H -6.153644 2.886474 -1.744792 H -4.754309 3.616574 -2.525563 C 4.298331 0.960076 0.286182 C 1.785730 -3.486702 -1.994527 C 3.959051 -0.052918 1.402695 H 4.653845 -0.901200 1.390050 H 2.956436 -0.475376 1.312976 H 4.026324 0.417325 2.390963 C 4.164939 0.299249 -1.101938 H 4.830041 -0.567463 -1.194045 H 4.425176 1.005506 -1.899389 H 3.154102 -0.056035 -1.306575 C 2.347852 -3.118641 -0.606969 H 1.865352 -3.703799 0.183449 H 2.217415 -2.063880 -0.365653 H 3.425605 -3.313665 -0.551389 C 2.440732 -2.605206 -3.082440 H 2.069484 -2.872854 -4.079033 H 3.530049 -2.729970 -3.088908 H 2.246331 -1.538881 -2.943098 C 2.275100 -4.933726 -2.272139 H 1.976779 -5.280170 -3.268616 H 1.889164 -5.640462 -1.528072 H 3.369724 -4.995630 -2.232030 C 5.807698 1.280364 0.457165 H 6.415150 0.369483 0.387084 H 6.018388 1.728566 1.435296 H 6.169427 1.961538 -0.322035 N -1.058250 -0.279597 0.940031 C -0.333372 -1.291609 1.600778 C -0.527586 0.086047 2.194921 H 0.660654 -1.547577 1.257437 H 0.391206 0.656641 2.285778 C -0.982208 -2.433593 2.385094 C -1.489533 0.201704 3.339960 C -3.387138 0.387916 5.422983 C -1.635405 1.385175 4.079022 C -2.299117 -0.889521 3.686151 C -3.248177 -0.799536 4.704429 C -2.579505 1.482842 5.112812 H -1.004435 2.243783 3.856527 H -3.874335 -1.656823 4.944890 H -4.125803 0.447696 6.221982 H -2.058848 -0.472292 0.914730 C -2.845346 -5.569959 -2.851883 C -2.064006 -6.900724 -2.939559
103
H -1.557639 -7.134056 -1.995635 H -1.311020 -6.875790 -3.735871 H -2.735528 -7.739098 -3.160845 C -3.918623 -5.748356 -1.755203 H -3.456836 -5.865468 -0.767508 H -4.532993 -6.636516 -1.943974 H -4.602131 -4.894203 -1.699160 C -3.539141 -5.357408 -4.214505 H -2.802692 -5.196511 -5.010747 H -4.210367 -4.491730 -4.208067 H -4.143788 -6.229283 -4.490384 C 3.787927 6.047591 0.908309 C 5.331175 6.038138 0.995601 H 5.724020 7.049899 1.153116 H 5.785348 5.657333 0.073377 H 5.684743 5.423366 1.831551 C 3.405995 6.984328 -0.258673 H 3.869479 7.970940 -0.141551 H 2.324621 7.145818 -0.325401 H 3.737029 6.572040 -1.219248 C 3.261927 6.643334 2.232393 H 3.719220 7.618651 2.436243 H 3.489702 5.984519 3.078771 H 2.177300 6.796024 2.217431 Cl 0.386009 1.576887 -2.446869 O -2.249465 -2.070352 2.993094 C -1.316824 -3.586233 1.433182 H -0.428619 -3.958757 0.915899 H -2.047580 -3.266087 0.683651 H -1.777858 -4.421049 1.973675 C -0.029000 -2.950714 3.473681 H 0.898845 -3.340098 3.040660 H -0.501505 -3.743995 4.063713 H 0.244286 -2.156287 4.176899 C -2.726831 2.725057 5.812002 N -2.825177 3.771881 6.299730 Table 3, Entry j Co -0.174174 0.587584 -0.885222 N -1.270042 2.311341 -0.889065 N -1.674671 -0.002098 -2.168364 C -0.720559 3.406401 -0.493668 H -1.352031 4.309742 -0.518783 C -1.854626 -1.258889 -2.383466 H -2.717569 -1.536025 -3.011087 C 0.670139 3.591621 -0.049146 C 3.228754 4.259405 0.804303 C 1.579572 2.569853 0.252282 C 1.053433 4.936761 0.078728 C 2.337394 5.300583 0.502868 C 2.889654 2.889331 0.699273 H 0.346743 5.733021 -0.156199 H 4.227023 4.530896 1.137186 C -1.026174 -2.364901 -1.882687 C 0.435032 -4.645844 -1.288044 C -1.605210 -3.635318 -2.019425 C 0.278017 -2.230685 -1.394851
C 1.067143 -3.385965 -1.150406 C -0.900351 -4.800501 -1.694849 H -2.624203 -3.734071 -2.393487 H 1.006559 -5.547423 -1.084283 C -2.642799 2.104974 -1.447209 H -3.220619 1.617435 -0.651450 C -2.476489 1.159874 -2.657226 H -1.867277 1.632460 -3.439853 O 1.257819 1.240968 0.211129 O 0.871602 -1.019819 -1.174259 C -3.840408 0.789714 -3.231765 H -3.729870 0.150032 -4.115462 H -4.431213 0.226093 -2.498004 C -3.354455 3.386653 -1.870300 H -2.749578 3.945957 -2.595735 H -3.514889 4.045387 -1.008553 C -4.715453 3.058487 -2.490693 H -5.185202 3.979587 -2.853844 H -5.375357 2.649747 -1.715206 C -4.606336 2.052395 -3.636028 H -5.609576 1.778545 -3.981693 H -4.096663 2.526985 -4.483874 C 3.944738 1.805579 1.064756 C 2.582046 -3.319381 -0.795110 C 3.437607 0.931536 2.233677 H 4.197460 0.202431 2.539392 H 2.541488 0.358464 1.987973 H 3.198082 1.548618 3.107884 C 4.254634 0.932297 -0.170251 H 5.014691 0.176396 0.060071 H 4.633515 1.544331 -0.997519 H 3.381050 0.395641 -0.543666 C 2.808127 -2.597449 0.547327 H 2.257982 -3.086943 1.358162 H 2.495944 -1.553504 0.519399 H 3.869610 -2.595791 0.822613 C 3.353952 -2.591360 -1.920229 H 3.198474 -3.086825 -2.886033 H 4.431970 -2.585533 -1.719462 H 3.054457 -1.547003 -2.039129 C 3.262642 -4.706716 -0.647899 H 3.193530 -5.292689 -1.571944 H 2.820169 -5.290304 0.167988 H 4.330234 -4.601325 -0.418238 C 5.312007 2.374585 1.530654 H 6.014063 1.567003 1.772600 H 5.209402 2.987339 2.433992 H 5.785961 2.982371 0.750928 N -1.225188 -0.084904 0.631265 C -0.597746 -0.942681 1.561469 C -1.040278 0.461024 1.917451 H 0.477027 -1.086515 1.535784 H -0.253721 1.178879 2.114794 H -2.188861 -0.339840 0.419765 C -1.428183 -2.055502 2.146305 C -3.094457 -4.102217 3.160967 C -1.028282 -3.398055 2.104180
104
C -2.668757 -1.765261 2.742652 C -3.506074 -2.770780 3.226171 C -1.849264 -4.412950 2.608054 H -0.068643 -3.673524 1.674944 H -4.470136 -2.510894 3.660069 H -1.512759 -5.448705 2.560257 C -2.157212 0.566710 2.950773 Cl 0.873677 1.356104 -2.606573 C -1.573801 -6.183005 -1.837181 C -1.901420 -6.439081 -3.323366 H -0.995348 -6.399689 -3.939606 H -2.603562 -5.699985 -3.724790 H -2.357446 -7.426100 -3.463335 C -2.881735 -6.220108 -1.015081 H -2.688474 -6.006543 0.042121 H -3.357121 -7.206354 -1.073444 H -3.619172 -5.491905 -1.369003 C -0.703591 -7.362023 -1.345533 H -0.426641 -7.244969 -0.291223 H 0.216517 -7.459871 -1.933233 H -1.240559 -8.313973 -1.436175 C 2.724233 6.790884 0.626381 C 2.578430 7.478737 -0.748638 H 2.880501 8.531413 -0.698045 H 1.546412 7.460213 -1.115395 H 3.204588 6.987779 -1.503063 C 1.791923 7.484096 1.643794 H 2.066016 8.537153 1.777454 H 1.848149 6.997528 2.624796 H 0.743493 7.464814 1.326993 C 4.175010 7.031589 1.102447 H 4.395517 8.103748 1.170637 H 4.904754 6.597335 0.409139 H 4.349927 6.604429 2.096786 O -3.149522 -0.479748 2.818082 C -1.589627 0.563737 4.378672 H -0.920347 1.414850 4.544984 H -1.016789 -0.347579 4.582317 H -2.395886 0.600954 5.119788 C -2.913045 1.883009 2.722958 H -2.247106 2.750066 2.789102 H -3.720311 2.003952 3.454272 H -3.385878 1.893586 1.734989 C -3.949816 -5.145908 3.643289 N -4.650835 -5.993448 4.009460 Table 3, Entry k Co -0.336460 0.406694 -0.803382 N -1.671656 1.754093 -0.043233 N -1.901614 0.053147 -2.086375 C -1.244841 2.716219 0.696379 H -2.007079 3.413356 1.080974 C -1.914405 -1.033789 -2.776460 H -2.795375 -1.202979 -3.417091 C 0.150545 3.007351 1.057344 C 2.668942 3.828600 1.891769 C 1.245338 2.156083 0.862079
C 0.328825 4.259141 1.669117 C 1.586598 4.697053 2.099569 C 2.541874 2.556428 1.283388 H -0.524566 4.920229 1.820450 H 3.650278 4.157714 2.222670 C -0.890348 -2.088088 -2.780112 C 0.896280 -4.185596 -3.090105 C -1.308093 -3.299311 -3.352847 C 0.423813 -1.935531 -2.324987 C 1.369233 -2.975898 -2.525359 C -0.432713 -4.381707 -3.497975 H -2.335105 -3.415659 -3.698422 H 1.592435 -5.007839 -3.231221 C -3.064438 1.481818 -0.502721 H -3.412908 0.620090 0.081992 C -2.947089 1.119067 -2.000029 H -2.555958 1.967250 -2.578543 O 1.131893 0.893135 0.347307 O 0.875879 -0.788037 -1.735938 C -4.309894 0.712181 -2.553279 H -4.245001 0.494046 -3.625879 H -4.672633 -0.199337 -2.060621 C -4.035118 2.643240 -0.311577 H -3.658825 3.549955 -0.802769 H -4.154511 2.879187 0.752626 C -5.408041 2.287823 -0.888179 H -6.075809 3.152929 -0.806785 H -5.853918 1.484569 -0.288300 C -5.326734 1.838043 -2.346416 H -6.315119 1.506862 -2.684630 H -5.047523 2.695110 -2.971968 C 3.801717 1.660020 1.108011 C 2.883078 -2.823662 -2.196242 C 3.652671 0.367152 1.938593 H 4.549389 -0.258802 1.859318 H 2.811190 -0.250962 1.621395 H 3.501007 0.598732 2.999660 C 4.019679 1.323687 -0.383527 H 4.931284 0.731351 -0.526606 H 4.119388 2.237945 -0.980637 H 3.202979 0.744041 -0.815867 C 3.097515 -2.551988 -0.695099 H 2.609700 -3.317355 -0.080741 H 2.709489 -1.580158 -0.390013 H 4.163763 -2.549052 -0.439039 C 3.487761 -1.672561 -3.032410 H 3.346057 -1.851213 -4.105008 H 4.564803 -1.576269 -2.850572 H 3.044191 -0.699835 -2.805071 C 3.737086 -4.077928 -2.523596 H 3.692665 -4.333025 -3.588937 H 3.414035 -4.950000 -1.942949 H 4.794369 -3.910647 -2.283164 C 5.125807 2.316774 1.583592 H 5.979430 1.646908 1.421611 H 5.104133 2.545472 2.655600 H 5.338634 3.242070 1.035340
105
N -1.028029 -0.974123 0.411262 C -0.122363 -1.778675 1.111710 C -0.962924 -0.706597 1.791966 H 0.940240 -1.592554 1.027708 H -0.372259 0.099710 2.211253 C -0.382543 -3.223533 1.421659 H 0.427121 -3.579150 2.071150 H -0.325450 -3.813317 0.499921 Cl 0.315868 1.934634 -2.179327 C -0.929664 -5.709171 -4.110213 C 0.144645 -6.818687 -4.173740 H 0.527413 -7.066893 -3.176896 H 0.992499 -6.525143 -4.803580 H -0.265773 -7.741818 -4.600560 C -2.099797 -6.262061 -3.266762 H -1.796051 -6.415059 -2.224318 H -2.448357 -7.225238 -3.657597 H -2.963903 -5.588886 -3.262072 C -1.415760 -5.461296 -5.554452 H -0.614512 -5.039886 -6.173060 H -2.261429 -4.766080 -5.594046 H -1.745759 -6.394345 -6.026035 C 1.742171 6.077548 2.773391 C 0.876447 6.126955 4.051579 H 1.159740 5.330810 4.750348 H -0.191046 6.009448 3.835456 H 0.993743 7.084906 4.571626 C 1.278385 7.183875 1.800963 H 1.852626 7.153796 0.867367 H 1.410580 8.178773 2.242125 H 0.219093 7.089419 1.538494 C 3.190396 6.418669 3.192059 H 3.866059 6.438653 2.329010 H 3.581878 5.696161 3.917664 H 3.242619 7.407405 3.663713 C -2.153458 -1.069091 2.655763 H -3.042929 -1.067918 2.010689 C -1.976165 -2.476096 3.241137 H -2.882387 -2.764243 3.786545 H -1.144597 -2.500292 3.956126 C -1.714267 -3.487189 2.123170 H -2.532672 -3.446169 1.393832 H -1.710265 -4.503111 2.534427 C -2.400078 -0.012743 3.744994 O -1.312612 0.080197 4.663547 C -1.119285 1.476893 4.904424 C -2.306316 2.153762 4.262357 O -2.605973 1.290977 3.152297 H -3.303575 -0.274034 4.311533 H -1.033690 1.679231 5.975044 H -0.186275 1.767914 4.410714 H -2.090740 3.167619 3.916268 H -3.175013 2.176228 4.929816 H -1.843588 -1.488528 0.085448 Table 3, Entry l Co -0.199148 0.626564 -0.219886
N -1.360065 2.282365 0.078342 N -1.758089 0.158196 -1.481562 C -0.818314 3.369323 0.503640 H -1.485212 4.239362 0.620548 C -1.740970 -0.949944 -2.130883 H -2.591559 -1.126171 -2.809177 C 0.597272 3.581881 0.831814 C 3.179977 4.282324 1.563499 C 1.548367 2.572060 1.015018 C 0.949678 4.930597 1.004078 C 2.247579 5.311517 1.363085 C 2.870216 2.908350 1.413481 H 0.205436 5.713888 0.860245 H 4.188156 4.565820 1.853062 C -0.717205 -1.999060 -2.091254 C 1.038056 -4.136819 -2.312499 C -1.088749 -3.166314 -2.781656 C 0.536160 -1.908704 -1.476181 C 1.463935 -2.980345 -1.612853 C -0.231656 -4.265382 -2.891396 H -2.071896 -3.235147 -3.247649 H 1.725172 -4.971609 -2.419257 C -2.780613 2.032600 -0.298518 H -3.193966 1.392662 0.490999 C -2.734028 1.283101 -1.641503 H -2.309268 1.925772 -2.425448 O 1.256879 1.241237 0.893830 O 0.948452 -0.845783 -0.720707 C -4.141861 0.853230 -2.048297 H -4.138147 0.357282 -3.025329 H -4.554333 0.138226 -1.326941 C -3.642622 3.285282 -0.416468 H -3.212172 3.988502 -1.141099 H -3.702693 3.809005 0.545044 C -5.059534 2.907026 -0.856485 H -5.653145 3.815889 -1.006440 H -5.546238 2.338136 -0.054331 C -5.066185 2.072208 -2.136583 H -6.088261 1.742564 -2.355083 H -4.749592 2.702479 -2.977109 C 3.972748 1.843228 1.677923 C 2.927327 -2.913612 -1.081892 C 3.524362 0.844956 2.768854 H 4.335933 0.155799 3.031693 H 2.685218 0.219437 2.460011 H 3.225374 1.370750 3.683235 C 4.290900 1.097655 0.367483 H 5.066852 0.338461 0.519785 H 4.647727 1.790300 -0.404073 H 3.418236 0.586517 -0.040382 C 2.975425 -2.607215 0.429517 H 2.316089 -3.279406 0.990471 H 2.688791 -1.581346 0.661696 H 3.989982 -2.727089 0.828451 C 3.692668 -1.830901 -1.873351 H 3.738750 -2.084052 -2.939560 H 4.722136 -1.729000 -1.510871
106
H 3.223870 -0.846012 -1.803412 C 3.735698 -4.227517 -1.260584 H 3.846009 -4.500316 -2.316646 H 3.264565 -5.064610 -0.732064 H 4.751934 -4.124546 -0.860152 C 5.322333 2.425648 2.176873 H 6.053980 1.628488 2.358117 H 5.202545 2.970932 3.120446 H 5.772313 3.101117 1.439864 N -1.036581 -0.190567 1.385964 C -1.344873 -1.549769 1.395779 C -0.189988 -0.976173 2.202270 H -1.051379 -2.211897 0.593350 H 0.806986 -1.244672 1.880611 C -2.561573 -2.109277 2.090611 H -2.446511 -3.202637 2.080831 Cl 0.650542 1.616175 -1.938445 C -0.685740 -5.537183 -3.638724 C 0.362128 -6.673329 -3.649326 H 0.619032 -6.994576 -2.633150 H 1.284896 -6.367499 -4.155983 H -0.016849 -7.555166 -4.179903 C -1.958650 -6.102539 -2.970008 H -1.780917 -6.327287 -1.911583 H -2.283249 -7.029040 -3.458014 H -2.800943 -5.403947 -3.020381 C -0.995889 -5.188732 -5.110466 H -0.118905 -4.755733 -5.606113 H -1.814869 -4.467022 -5.202406 H -1.290981 -6.081449 -5.674247 C 2.602889 6.804299 1.535562 C 1.728527 7.417556 2.650862 H 1.869115 6.885423 3.599198 H 0.660785 7.381113 2.408802 H 1.982766 8.470748 2.818362 C 2.340053 7.555414 0.211851 H 2.922142 7.121228 -0.609691 H 2.617976 8.612648 0.295317 H 1.284946 7.525295 -0.080965 C 4.077657 7.064350 1.918647 H 4.766137 6.682178 1.155933 H 4.334402 6.598353 2.877131 H 4.275555 8.138163 2.021397 C -0.284189 -0.878270 3.698563 H -0.524972 0.152156 3.986964 C -1.321457 -1.835719 4.277222 H -1.444164 -1.633985 5.347273 H -0.967788 -2.869809 4.182433 C -2.664585 -1.687984 3.565560 H -3.005341 -0.648049 3.645775 H -3.413710 -2.306300 4.074163 H 0.694457 -1.101120 4.139513 C -3.847106 -1.763296 1.317745 O -3.701657 -2.069281 -0.089430 C -4.485048 -3.261461 -0.258030 C -5.602231 -3.084966 0.734172 O -4.956387 -2.482281 1.853592
H -4.060345 -0.691265 1.389948 H -4.828874 -3.349626 -1.291409 H -3.851561 -4.120101 -0.010393 H -6.358891 -2.384805 0.364415 H -6.083394 -4.023206 1.020389 H -1.612969 0.435084 1.944941 Table 3, Entry m Co -0.455975 0.403269 -0.465004 N -1.443429 2.207634 -0.303552 N -2.187656 -0.044637 -1.530730 C -0.762766 3.274995 -0.073760 H -1.330024 4.219228 -0.026775 C -2.315903 -1.204348 -2.068041 H -3.233558 -1.363868 -2.657593 C 0.690164 3.372194 0.124227 C 3.373372 3.889050 0.609494 C 1.554043 2.299600 0.377657 C 1.180869 4.688260 0.099112 C 2.531174 4.975318 0.328696 C 2.925492 2.546324 0.657500 H 0.505844 5.520834 -0.099877 H 4.421229 4.101583 0.803237 C -1.376679 -2.330286 -2.014271 C 0.176884 -4.626816 -2.172157 C -1.880677 -3.502319 -2.606890 C -0.085906 -2.311450 -1.473945 C 0.733506 -3.472775 -1.567833 C -1.124564 -4.676029 -2.688515 H -2.888868 -3.516277 -3.022706 H 0.783632 -5.524412 -2.254143 C -2.912892 2.057557 -0.509635 H -3.298104 1.575146 0.395813 C -3.077181 1.144602 -1.733871 H -2.691898 1.640534 -2.635930 O 1.139480 0.997352 0.437834 O 0.465508 -1.243524 -0.823019 C -4.552277 0.803166 -1.935639 H -4.699205 0.192685 -2.833565 H -4.935999 0.221602 -1.088502 C -3.668055 3.366209 -0.717825 H -3.262000 3.919948 -1.574145 H -3.573572 4.015494 0.160738 C -5.153246 3.077898 -0.955087 H -5.679519 4.014047 -1.173203 H -5.593006 2.673254 -0.034851 C -5.378219 2.084546 -2.094746 H -6.442398 1.829928 -2.155973 H -5.112539 2.565282 -3.044702 C 3.936787 1.416008 1.005974 C 2.218364 -3.509822 -1.094652 C 3.465298 0.618480 2.242939 H 4.224718 -0.106905 2.558741 H 2.555951 0.043132 2.060867 H 3.270623 1.286312 3.090314 C 4.098066 0.477100 -0.204901 H 4.813421 -0.326143 0.006720
107
H 4.459728 1.024215 -1.083610 H 3.158278 0.001476 -0.487028 C 2.368100 -3.061705 0.375424 H 1.660638 -3.590872 1.024041 H 2.215075 -1.990367 0.510318 H 3.378414 -3.262172 0.752252 C 3.050596 -2.597477 -2.020704 H 3.030181 -2.964181 -3.054214 H 4.098600 -2.559537 -1.701871 H 2.677452 -1.570245 -2.044322 C 2.878197 -4.914007 -1.163025 H 2.927168 -5.295275 -2.189652 H 2.337714 -5.642004 -0.546681 H 3.912033 -4.883983 -0.797055 C 5.364662 1.916237 1.352737 H 6.027384 1.078339 1.602429 H 5.357848 2.588004 2.219166 H 5.828658 2.441074 0.509429 N -1.196813 -0.094417 1.247859 C -1.672867 -1.411485 1.463937 C -0.460289 -0.843909 2.182831 H -1.433309 -2.234696 0.806537 H 0.490652 -1.267242 1.872514 C -3.091940 -1.437146 1.910101 C -0.498490 -0.439357 3.638587 C -0.506993 0.300257 6.368512 C -0.195896 0.873614 4.044891 C -0.775391 -1.374804 4.649515 C -0.788561 -1.010387 5.998364 C -0.204797 1.243309 5.392244 H 0.067247 1.624263 3.306000 H -0.981320 -2.413222 4.395459 H -1.008791 -1.753376 6.762439 H 0.035682 2.262587 5.685983 H -0.509199 0.581296 7.419765 H -1.742317 0.630954 1.713151 C -1.717431 -5.943654 -3.341118 C -0.766343 -7.162185 -3.336578 H -0.486870 -7.452009 -2.316918 H 0.152191 -6.960136 -3.899802 H -1.240769 -8.035215 -3.800830 C -2.996192 -6.365847 -2.584560 H -2.784121 -6.549788 -1.524614 H -3.418564 -7.286099 -3.004909 H -3.780681 -5.603048 -2.635355 C -2.071926 -5.648290 -4.814632 H -1.188940 -5.315928 -5.373325 H -2.834070 -4.867203 -4.909769 H -2.465432 -6.541831 -5.313259 C 3.037288 6.433539 0.283919 C 4.554277 6.585708 0.538719 H 4.859812 7.637750 0.487226 H 5.145287 6.042285 -0.207735 H 4.835956 6.219011 1.532675 C 2.749452 7.039405 -1.107356 H 3.131530 8.064519 -1.178857 H 1.677494 7.082691 -1.328514
H 3.225507 6.449828 -1.899849 C 2.309238 7.265633 1.361856 H 2.672923 8.299773 1.375449 H 2.468938 6.842556 2.360746 H 1.227823 7.309236 1.192599 Cl 0.329910 1.064973 -2.361671 O -3.932745 -0.816269 1.267809 O -3.292652 -2.244144 2.972137 C -4.645114 -2.295893 3.432729 H -4.993115 -1.296241 3.711102 H -4.677484 -2.935350 4.318973 H -5.290820 -2.730496 2.663564 Table 3, Entry n Co -0.202922 0.675439 -0.691269 N -1.030670 2.533356 -0.342599 N -1.893620 0.513739 -1.868368 C -0.279178 3.475481 0.109962 H -0.765405 4.449357 0.285419 C -2.260511 -0.647419 -2.283717 H -3.186347 -0.686895 -2.880844 C 1.168493 3.406329 0.371092 C 3.886943 3.603840 0.916080 C 1.944205 2.239886 0.422009 C 1.765240 4.658323 0.592807 C 3.132924 4.786353 0.864855 C 3.333603 2.317775 0.708680 H 1.163155 5.566534 0.554228 H 4.948504 3.692018 1.131196 C -1.586245 -1.928737 -2.039278 C -0.517333 -4.479700 -1.844311 C -2.364299 -3.054340 -2.356204 C -0.269177 -2.080587 -1.592076 C 0.314674 -3.374833 -1.538496 C -1.857026 -4.353239 -2.242017 H -3.391714 -2.931206 -2.698948 H -0.103547 -5.482581 -1.783931 C -2.466967 2.594356 -0.750725 H -3.031669 2.061680 0.022136 C -2.555337 1.837841 -2.091901 H -1.958579 2.341403 -2.864757 O 1.421678 0.982291 0.285659 O 0.531592 -1.027815 -1.249085 C -4.007751 1.745648 -2.552519 H -4.076206 1.249958 -3.528116 H -4.601686 1.150554 -1.846653 C -3.023312 4.007281 -0.896756 H -2.418649 4.592813 -1.601422 H -3.000094 4.535271 0.064001 C -4.471280 3.958968 -1.391366 H -4.836797 4.978504 -1.558348 H -5.104290 3.518104 -0.611105 C -4.618561 3.144303 -2.675734 H -5.679235 3.059972 -2.938102 H -4.129219 3.679664 -3.499016 C 4.249121 1.062645 0.802035 C 1.818883 -3.618316 -1.216288
108
C 3.779833 0.142686 1.950880 H 4.446096 -0.721103 2.061817 H 2.775511 -0.257534 1.799069 H 3.772442 0.681939 2.905634 C 4.244505 0.296791 -0.538620 H 4.918608 -0.567280 -0.503403 H 4.574082 0.943314 -1.360638 H 3.259513 -0.087995 -0.806518 C 2.186516 -3.082870 0.180821 H 1.516435 -3.487216 0.947989 H 2.143323 -1.994848 0.234095 H 3.211625 -3.358514 0.456115 C 2.694652 -2.933843 -2.290443 H 2.459707 -3.317777 -3.290422 H 3.760057 -3.115804 -2.105957 H 2.561088 -1.849467 -2.322196 C 2.239109 -5.112853 -1.215437 H 2.074791 -5.582567 -2.192342 H 1.692382 -5.685556 -0.457044 H 3.307002 -5.223682 -0.989655 C 5.739929 1.378654 1.098319 H 6.336799 0.459346 1.145556 H 5.863542 1.885688 2.062490 H 6.184563 2.005771 0.316620 N -1.168528 -0.052419 0.862441 C -0.560750 -0.982945 1.720772 C -0.814302 0.452253 2.148485 H 0.483498 -1.225025 1.550990 H 0.082408 1.036079 2.309761 H -2.171100 -0.183980 0.735688 C -1.351448 -2.108363 2.351408 C -2.752865 -4.239899 3.580822 C -2.363281 -2.809074 1.674246 C -1.055388 -2.526746 3.662053 C -1.748198 -3.574711 4.273376 C -3.060003 -3.859201 2.279454 H -2.621994 -2.548151 0.655500 H -0.270620 -2.029130 4.229876 H -1.500108 -3.874438 5.289601 H -3.839966 -4.387478 1.736171 H -3.290613 -5.058809 4.054143 C -1.968427 0.952407 2.945543 Cl 0.762399 1.510633 -2.430074 C -2.747041 -5.570492 -2.573269 C -3.199610 -5.494079 -4.047434 H -2.336833 -5.463735 -4.723413 H -3.807014 -4.605193 -4.249732 H -3.806673 -6.365262 -4.320211 C -3.990929 -5.565756 -1.657756 H -3.701146 -5.595333 -0.601000 H -4.628526 -6.436040 -1.852682 H -4.612423 -4.675696 -1.803793 C -2.049763 -6.936423 -2.380240 H -1.718065 -7.077234 -1.344863 H -1.178470 -7.041972 -3.037077 H -2.729994 -7.763817 -2.615805 C 3.753546 6.181447 1.097989
C 3.539242 7.058853 -0.154762 H 4.001386 8.045197 -0.030321 H 2.478058 7.228265 -0.367122 H 3.982145 6.592465 -1.042788 C 3.074719 6.852716 2.311833 H 3.519915 7.832287 2.521979 H 3.181523 6.237358 3.213053 H 2.003667 7.016673 2.150871 C 5.272862 6.159617 1.381822 H 5.660252 7.173850 1.536935 H 5.833643 5.726255 0.545459 H 5.506656 5.585445 2.285944 O -2.733810 1.770829 2.449088 O -1.975576 0.473313 4.206930 C -3.072393 0.920672 5.007097 H -4.023657 0.642427 4.542768 H -3.016005 2.003323 5.155688 H -3.003895 0.429738 5.981616 Table 4, Top, Quadrant I/II Co 0.475490 0.401669 -0.344599 N 2.060328 1.733719 -0.111534 N -0.183551 1.826928 -1.710680 C 3.173208 1.340069 0.398548 H 3.969422 2.098463 0.479008 C -1.315890 1.694239 -2.304447 H -1.588691 2.489977 -3.016720 C 3.499234 -0.012055 0.870787 C 4.399236 -2.443571 1.855761 C 2.580004 -1.051599 1.057438 C 4.857568 -0.200460 1.174138 C 5.338549 -1.418395 1.667315 C 3.018780 -2.301173 1.570759 H 5.569218 0.612474 1.029703 H 4.761299 -3.391769 2.243758 C -2.266561 0.583450 -2.173268 C -4.193829 -1.409406 -2.236273 C -3.481911 0.787071 -2.846682 C -2.022215 -0.619054 -1.499878 C -2.982006 -1.664743 -1.548503 C -4.477449 -0.195364 -2.879637 H -3.671237 1.727908 -3.363827 H -4.948496 -2.189959 -2.281072 C 1.640821 3.072344 -0.626666 H 0.966372 3.492000 0.129116 C 0.901124 2.837005 -1.953572 H 1.570718 2.376204 -2.692956 O 1.247690 -0.901922 0.806356 O -0.894462 -0.836501 -0.767393 C 0.372413 4.161284 -2.508001 H -0.103178 4.014567 -3.484707 H -0.391005 4.581412 -1.840494 C 2.809057 4.037375 -0.824658 H 3.558058 3.606535 -1.501879 H 3.314161 4.236206 0.128240 C 2.312456 5.365674 -1.397724 H 3.166163 6.024253 -1.593523
109
H 1.685557 5.870059 -0.651810 C 1.509167 5.171280 -2.680892 H 1.099015 6.133510 -3.007822 H 2.180289 4.825127 -3.476902 C 2.062101 -3.501178 1.819117 C -2.737527 -3.072911 -0.933978 C 0.972238 -3.119939 2.842952 H 0.333350 -3.979023 3.079956 H 0.308617 -2.333373 2.483332 H 1.419117 -2.768296 3.780372 C 1.421085 -3.940879 0.487909 H 0.750641 -4.796063 0.632883 H 2.186667 -4.236226 -0.239430 H 0.829962 -3.148854 0.027489 C -2.389348 -2.985616 0.566141 H -3.123933 -2.379421 1.108561 H -1.402884 -2.557732 0.743929 H -2.369899 -3.979395 1.029552 C -1.593797 -3.760689 -1.710152 H -1.864001 -3.900808 -2.763880 H -1.368213 -4.747895 -1.290544 H -0.666966 -3.181272 -1.696386 C -3.955400 -4.031616 -1.020574 H -4.239863 -4.239496 -2.058699 H -4.827213 -3.622768 -0.496360 H -3.728648 -5.001786 -0.561256 C 2.751427 -4.767679 2.394210 H 2.026637 -5.577052 2.546719 H 3.215938 -4.569424 3.367327 H 3.519545 -5.156327 1.715267 C -0.975140 0.420247 2.137383 H -1.158800 -0.632036 1.955972 C -1.807573 1.369845 1.299279 H -2.485077 0.860026 0.623283 Cl 1.548457 -0.460570 -2.004495 C -2.388343 2.644380 1.871936 C -3.549150 4.999335 2.926854 C -2.051491 3.915071 1.373678 C -3.345164 2.594503 2.901427 C -3.915525 3.755599 3.428476 C -2.618816 5.080939 1.896376 H -1.340113 4.011477 0.564635 H -3.660192 1.634387 3.307910 H -4.649759 3.688254 4.229188 H -2.343879 6.056819 1.502678 H -3.995430 5.903170 3.337256 C -0.660041 0.653654 3.580760 H -1.487980 0.308301 4.207431 H -0.468652 1.706174 3.811654 H 0.232754 0.084325 3.858482 C -5.808001 0.067103 -3.617997 C -6.815177 -1.103071 -3.543467 H -7.086003 -1.336775 -2.507202 H -6.413882 -2.012033 -4.006596 H -7.744528 -0.858505 -4.071943 C -5.525462 0.330676 -5.112870 H -5.002998 -0.517674 -5.570690
H -4.905522 1.220499 -5.267521 H -6.456767 0.488669 -5.669283 C -6.504834 1.302372 -3.005963 H -6.688030 1.160547 -1.934219 H -7.471582 1.490079 -3.487752 H -5.909687 2.214894 -3.119876 C 6.839220 -1.592570 1.986896 C 7.215937 -2.995676 2.514827 H 6.978274 -3.778678 1.785297 H 6.694423 -3.228690 3.450507 H 8.290855 -3.064479 2.721262 C 7.671937 -1.350967 0.708817 H 7.374245 -2.039135 -0.091233 H 8.740935 -1.502793 0.898910 H 7.557892 -0.331418 0.324849 C 7.258866 -0.572837 3.067988 H 6.662820 -0.697614 3.979818 H 7.134218 0.462656 2.733039 H 8.313842 -0.696213 3.339502 N -0.407315 1.238543 1.136902 H 0.081684 2.000078 1.608575 Table 4, Top, Quadrant II/III Co 0.468200 0.689534 -0.679833 N 2.034672 2.068749 -0.450338 N -0.259202 2.131049 -2.005378 C 3.136272 1.708078 0.107579 H 3.919374 2.480508 0.180191 C -1.413323 1.988125 -2.555321 H -1.719295 2.777036 -3.261730 C 3.467390 0.388861 0.662609 C 4.346832 -1.952511 1.868656 C 2.581845 -0.684913 0.792295 C 4.789915 0.274151 1.121976 C 5.261440 -0.898201 1.724915 C 3.003717 -1.882810 1.427256 H 5.480696 1.110979 1.017992 H 4.696369 -2.862492 2.348800 C -2.350148 0.869579 -2.379770 C -4.259411 -1.143356 -2.340698 C -3.606243 1.067557 -2.974634 C -2.054129 -0.338612 -1.738212 C -3.003081 -1.394092 -1.738248 C -4.593047 0.074656 -2.953684 H -3.834784 2.009877 -3.472595 H -5.008206 -1.930976 -2.342070 C 1.637048 3.385558 -1.038442 H 1.018775 3.880169 -0.283425 C 0.834910 3.111317 -2.322137 H 1.466373 2.613594 -3.070678 O 1.294712 -0.634375 0.359018 O -0.873210 -0.560740 -1.099393 C 0.311643 4.423636 -2.907959 H -0.221432 4.248780 -3.849641 H -0.400706 4.895891 -2.219029 C 2.827720 4.296112 -1.344733 H 3.527969 3.801282 -2.030176
110
H 3.384944 4.531270 -0.430155 C 2.349208 5.611179 -1.964099 H 3.214671 6.224170 -2.240075 H 1.784405 6.178537 -1.213770 C 1.467758 5.386353 -3.189716 H 1.070138 6.346159 -3.538519 H 2.081656 4.982287 -4.004444 C 2.051276 -3.088685 1.668214 C -2.699190 -2.801228 -1.149547 C 0.877952 -2.660303 2.577842 H 0.211354 -3.505503 2.786400 H 0.259245 -1.873998 2.139991 H 1.246365 -2.282044 3.538983 C 1.521327 -3.631569 0.325369 H 0.887494 -4.513457 0.476158 H 2.346954 -3.922894 -0.334602 H 0.916465 -2.902598 -0.214413 C -2.354818 -2.712391 0.351296 H -3.178347 -2.257549 0.913229 H -1.458033 -2.125458 0.552156 H -2.175028 -3.707521 0.775473 C -1.534828 -3.444072 -1.935139 H -1.795853 -3.561844 -2.993900 H -1.292343 -4.437706 -1.540421 H -0.617051 -2.852930 -1.899485 C -3.878990 -3.805701 -1.246497 H -4.171881 -3.990970 -2.286631 H -4.758616 -3.450575 -0.696787 H -3.605757 -4.778001 -0.818024 C 2.715440 -4.298695 2.378008 H 1.997440 -5.115890 2.520351 H 3.090385 -4.030364 3.372696 H 3.547599 -4.705673 1.791588 C -1.772983 1.422656 1.112378 H -2.466637 1.537418 0.290414 C -0.754998 2.543408 1.268610 H -0.889255 3.308724 0.509275 Cl 1.533428 -0.015956 -2.416655 C -0.362062 3.097333 2.620465 C 0.340411 4.236813 5.114159 C 0.835988 2.753937 3.273646 C -1.193994 4.033268 3.261754 C -0.850092 4.596884 4.492980 C 1.183597 3.312920 4.506746 H 1.506887 2.017616 2.844071 H -2.137665 4.329627 2.806401 H -1.516265 5.311207 4.973406 H 2.104493 3.018665 5.006028 H 0.603035 4.667164 6.078788 C -2.469265 0.825204 2.294938 H -3.265632 1.493271 2.637621 H -1.796369 0.634039 3.136728 H -2.928340 -0.125855 2.012084 C -5.969360 0.329434 -3.606291 C -6.959667 -0.850359 -3.477319 H -7.163196 -1.093210 -2.427842 H -6.580213 -1.752610 -3.970972
H -7.922286 -0.610889 -3.945092 C -5.782212 0.604734 -5.113967 H -5.281866 -0.236056 -5.608931 H -5.180631 1.500995 -5.300653 H -6.747503 0.757819 -5.610617 C -6.637786 1.554468 -2.944154 H -6.752881 1.404488 -1.864083 H -7.634192 1.736113 -3.363846 H -6.058995 2.473131 -3.088781 C 6.723563 -0.990448 2.212982 C 7.097137 -2.352899 2.840253 H 6.969603 -3.174558 2.125827 H 6.488665 -2.570577 3.725768 H 8.145728 -2.365614 3.161330 C 7.682234 -0.761919 1.023789 H 7.503135 -1.493799 0.227205 H 8.728885 -0.857709 1.335722 H 7.570430 0.235546 0.585110 C 6.977995 0.089748 3.286721 H 6.290623 -0.026365 4.133082 H 6.847490 1.104149 2.894330 H 8.000764 0.026554 3.676397 N -0.402578 1.232206 0.899575 H -0.050608 0.717466 1.711351 Table 4, Top, Quadrant III/IV Co 0.409643 0.486643 -0.755953 N 1.939890 1.868864 -0.439152 N -0.221057 1.894910 -2.170608 C 3.005113 1.519095 0.192964 H 3.767142 2.303209 0.334371 C -1.389835 1.801317 -2.700744 H -1.658814 2.574389 -3.439236 C 3.332199 0.181545 0.709355 C 4.246798 -2.237398 1.717715 C 2.457602 -0.910776 0.761436 C 4.651770 0.054098 1.172756 C 5.136976 -1.152904 1.689461 C 2.908016 -2.160932 1.262371 H 5.330339 0.906378 1.136965 H 4.614557 -3.179969 2.113969 C -2.403834 0.777918 -2.415542 C -4.478940 -1.033366 -2.108046 C -3.688587 1.083819 -2.889500 C -2.154918 -0.440406 -1.772303 C -3.196119 -1.392029 -1.626632 C -4.756662 0.192723 -2.733882 H -3.876090 2.032778 -3.391371 H -5.297085 -1.740226 -1.998912 C 1.568179 3.171534 -1.082768 H 0.854916 3.653779 -0.403257 C 0.900306 2.853806 -2.434500 H 1.596996 2.328491 -3.101110 O 1.148318 -0.812492 0.397797 O -0.913480 -0.774768 -1.313578 C 0.433050 4.141145 -3.114418 H 0.001697 3.925966 -4.099312
111
H -0.351343 4.628699 -2.520723 C 2.764173 4.102788 -1.283034 H 3.545523 3.607195 -1.873940 H 3.212760 4.371478 -0.319161 C 2.333615 5.389165 -1.990334 H 3.212861 6.013620 -2.185071 H 1.676016 5.963902 -1.326245 C 1.603107 5.108843 -3.300993 H 1.237459 6.049895 -3.727225 H 2.310304 4.685262 -4.025009 C 2.007172 -3.427794 1.322683 C -2.979222 -2.791662 -0.987723 C 0.846391 -3.205877 2.312375 H 0.218784 -4.101049 2.394880 H 0.189515 -2.387948 2.013265 H 1.223809 -2.970338 3.314544 C 1.458908 -3.766717 -0.080160 H 0.872795 -4.693318 -0.063823 H 2.275429 -3.901430 -0.799389 H 0.800817 -2.992824 -0.476540 C -2.454917 -2.653450 0.455624 H -3.122673 -2.029004 1.060755 H -1.461656 -2.207700 0.498204 H -2.376031 -3.631033 0.945862 C -1.986904 -3.606179 -1.845734 H -2.370822 -3.742450 -2.863958 H -1.818764 -4.601373 -1.417566 H -1.008332 -3.129208 -1.935580 C -4.263457 -3.657006 -0.884810 H -4.692541 -3.867740 -1.871431 H -5.029961 -3.171294 -0.269495 H -4.049444 -4.627939 -0.421041 C 2.736542 -4.711223 1.803704 H 2.060192 -5.575052 1.800178 H 3.107526 -4.608177 2.830196 H 3.581482 -4.964411 1.152532 C -1.549444 2.105196 0.754696 H -1.442829 2.958777 0.097503 C -0.391207 1.892239 1.728699 H 0.425202 2.595697 1.614259 Cl 1.661410 -0.226060 -2.361685 C -0.626913 1.502270 3.171395 C -1.010151 0.824196 5.892039 C -0.090481 0.324766 3.717093 C -1.340283 2.343322 4.044507 C -1.536890 2.007654 5.386808 C -0.283056 -0.017609 5.058055 H 0.490128 -0.345931 3.094649 H -1.758457 3.280821 3.683958 H -2.100739 2.670412 6.040264 H 0.134486 -0.940565 5.454662 H -1.163627 0.560678 6.936549 C -2.983644 1.931446 1.153137 H -3.336213 2.819605 1.686337 H -3.146621 1.057353 1.791424 H -3.605878 1.812341 0.261440 C -6.163405 0.564802 -3.250418
C -7.239317 -0.514439 -2.992041 H -7.359384 -0.716381 -1.921244 H -6.994069 -1.457764 -3.493780 H -8.217804 -0.195230 -3.370801 C -6.109358 0.797409 -4.775897 H -5.741310 -0.094035 -5.297555 H -5.451932 1.630997 -5.045893 H -7.103074 1.031407 -5.175491 C -6.643133 1.857683 -2.554645 H -6.659275 1.735905 -1.465018 H -7.656340 2.126727 -2.875498 H -5.999132 2.714669 -2.779983 C 6.592556 -1.255577 2.195026 C 6.977279 -2.650009 2.739900 H 6.884178 -3.424433 1.969591 H 6.351056 -2.937126 3.592658 H 8.017821 -2.665439 3.086068 C 7.565044 -0.936041 1.038750 H 7.410597 -1.618096 0.194226 H 8.608290 -1.034825 1.360935 H 7.442327 0.085521 0.662855 C 6.814425 -0.244284 3.340991 H 6.114892 -0.424086 4.165983 H 6.676968 0.791920 3.013401 H 7.831426 -0.319733 3.743420 N -0.699995 1.000476 0.676470 H -1.171725 0.181595 1.075396 Table 4, Top, Quadrant IV/I Co 0.594948 0.543395 -0.495784 N 2.081954 1.945052 -0.145915 N -0.065098 1.973383 -1.872594 C 3.194975 1.585070 0.390572 H 3.951177 2.375744 0.527415 C -1.224625 1.864799 -2.417761 H -1.514987 2.668542 -3.114238 C 3.572145 0.227593 0.816395 C 4.557092 -2.208278 1.710998 C 2.699854 -0.864147 0.927527 C 4.927975 0.086909 1.151921 C 5.451085 -1.131399 1.601383 C 3.180819 -2.116475 1.390665 H 5.605004 0.936941 1.066471 H 4.952735 -3.157014 2.063663 C -2.199237 0.785918 -2.215138 C -4.190915 -1.139257 -2.115587 C -3.466455 1.043784 -2.761887 C -1.933082 -0.435550 -1.586186 C -2.923051 -1.452509 -1.567011 C -4.496138 0.098226 -2.703141 H -3.671189 1.999702 -3.243931 H -4.973958 -1.892308 -2.093114 C 1.627399 3.270886 -0.666590 H 0.876472 3.637709 0.045628 C 0.998527 3.015566 -2.049278 H 1.733418 2.578144 -2.738816 O 1.366068 -0.762031 0.654823
112
O -0.736072 -0.709009 -0.998699 C 0.461439 4.319462 -2.641114 H 0.066321 4.153403 -3.650448 H -0.366488 4.706856 -2.032817 C 2.756922 4.295389 -0.767138 H 3.578269 3.907960 -1.384204 H 3.173993 4.509222 0.224442 C 2.245871 5.601933 -1.375472 H 3.080017 6.302102 -1.497348 H 1.534827 6.070469 -0.683717 C 1.564594 5.376138 -2.722692 H 1.142735 6.320572 -3.084674 H 2.314402 5.059738 -3.458492 C 2.270971 -3.366738 1.552539 C -2.659607 -2.885372 -1.021384 C 1.167530 -3.091232 2.595995 H 0.543751 -3.978713 2.755779 H 0.493495 -2.286052 2.301010 H 1.602996 -2.811724 3.562738 C 1.646674 -3.748664 0.194287 H 1.026844 -4.648846 0.281561 H 2.423791 -3.949900 -0.552651 H 1.005537 -2.965448 -0.211393 C -2.214978 -2.852864 0.453837 H -2.920311 -2.280967 1.067266 H -1.225166 -2.415191 0.581280 H -2.152923 -3.864029 0.873760 C -1.576946 -3.566429 -1.887748 H -1.901958 -3.642721 -2.932418 H -1.364870 -4.580903 -1.530273 H -0.629057 -3.022219 -1.887859 C -3.894571 -3.824817 -1.063652 H -4.256594 -3.977093 -2.087215 H -4.719860 -3.433254 -0.457311 H -3.649677 -4.818267 -0.667786 C 3.009581 -4.639459 2.046926 H 2.319311 -5.487675 2.134604 H 3.455621 -4.490973 3.037382 H 3.800780 -4.944907 1.352128 C -0.033949 1.428018 2.202963 H 0.864274 0.917246 2.533867 C -1.182433 0.507817 1.819833 H -0.944968 -0.550968 1.834621 Cl 1.812342 -0.245987 -2.091523 C -2.589344 0.820120 2.286776 C -5.214232 1.327339 3.220021 C -3.618272 1.205098 1.411822 C -2.927959 0.681837 3.645856 C -4.220831 0.936602 4.110451 C -4.914812 1.458965 1.868705 H -3.424213 1.305472 0.351894 H -2.174772 0.364398 4.365128 H -4.454531 0.822284 5.167046 H -5.696084 1.751439 1.170968 H -6.222977 1.519797 3.579427 C -0.231881 2.688966 2.983640 H -0.325634 2.462666 4.050176
H -1.117640 3.249930 2.669544 H 0.637822 3.340906 2.853274 C -5.888169 0.423858 -3.285843 C -6.923460 -0.712709 -3.126204 H -7.088904 -0.962522 -2.071654 H -6.608128 -1.623102 -3.649158 H -7.895026 -0.423549 -3.544807 C -5.761499 0.716316 -4.796464 H -5.322679 -0.136751 -5.327467 H -5.131128 1.588992 -4.999050 H -6.741839 0.919093 -5.243344 C -6.467525 1.665711 -2.572838 H -6.539314 1.501048 -1.491168 H -7.472763 1.900464 -2.942018 H -5.853650 2.559362 -2.729180 C 6.949045 -1.252147 1.957821 C 7.376092 -2.659901 2.432345 H 7.196888 -3.417664 1.660682 H 6.839291 -2.960426 3.339703 H 8.446655 -2.689117 2.668656 C 7.804810 -0.913142 0.717686 H 7.562111 -1.575820 -0.121497 H 8.874031 -1.024904 0.932663 H 7.653815 0.117053 0.377370 C 7.290202 -0.266390 3.096540 H 6.675172 -0.460675 3.983254 H 7.127075 0.777026 2.805629 H 8.341716 -0.354612 3.393957 N -0.499715 1.329992 0.880341 H -1.093114 2.124396 0.640030 Table 4, Bottom, Quadrant I/II C -2.430688 0.601950 2.353767 C -2.053319 2.827113 3.482738 C -3.958675 1.344217 4.225448 C -3.462479 2.777392 4.068759 C -3.854802 0.559255 2.918927 C -1.975986 2.057948 2.161098 H -1.342787 2.408206 4.206890 H -3.368701 0.838429 4.999928 H -4.148083 3.330160 3.414639 H -2.626581 2.561042 1.431625 H -1.770385 3.874992 3.328377 H -4.998802 1.349526 4.570338 H -3.475149 3.280824 5.042001 H -1.770614 0.094880 3.063082 N -2.314900 -0.055524 1.078880 H -4.564473 0.968278 2.188463 N -0.644424 2.023556 1.615644 H -4.156557 -0.476839 3.110987 C -3.111106 -0.937683 0.487040 H -3.975245 -1.327886 1.051227 C -2.976069 -1.413019 -0.896586 C -3.008963 -2.473129 -3.459302 C -1.836428 -1.291366 -1.694573 C -4.123236 -2.060283 -1.388090 C -4.170127 -2.599870 -2.675018
113
C -1.828376 -1.834785 -3.009576 H -4.991199 -2.126839 -0.737044 H -3.044301 -2.895404 -4.459813 C 0.455093 2.709706 1.903211 H 0.430321 3.414629 2.751612 C 1.725950 2.616435 1.174936 C 4.201603 2.794218 -0.070894 C 2.803226 3.251937 1.810367 C 1.894518 2.030330 -0.079090 C 3.139829 2.153431 -0.757647 C 4.068255 3.337783 1.216280 H 2.644583 3.689389 2.794404 H 5.166653 2.879799 -0.557668 O -0.687251 -0.720524 -1.235809 O 0.894401 1.353624 -0.706096 Co -0.618804 0.590039 0.134243 Cl -1.816155 1.862519 -1.135887 C 3.355790 1.647323 -2.209058 C 2.384929 2.373510 -3.167417 H 2.542317 3.458380 -3.134918 H 1.333594 2.195964 -2.929914 H 2.534600 2.046912 -4.203344 C 4.777842 1.912479 -2.773244 H 5.012968 2.983117 -2.795694 H 4.868757 1.546677 -3.803569 H 5.548779 1.400102 -2.185716 C 3.153248 0.122284 -2.293676 H 3.818760 -0.403674 -1.599577 H 3.363047 -0.251225 -3.303019 H 2.132436 -0.177555 -2.059842 C -0.595619 -1.752131 -3.946538 C -0.823341 -2.358246 -5.358019 H 0.075728 -2.261032 -5.979200 H -1.635449 -1.849779 -5.890994 H -1.058072 -3.428041 -5.308246 C -0.201586 -0.280302 -4.188968 H 0.646455 -0.205178 -4.879894 H 0.093943 0.235876 -3.275616 H -1.036103 0.283202 -4.623060 C 0.583800 -2.539937 -3.338770 H 1.459695 -2.511805 -3.997626 H 0.315143 -3.592289 -3.187054 H 0.904175 -2.149851 -2.371903 C 5.226768 4.025999 1.961521 C 6.566229 4.017179 1.190074 H 7.358916 4.506028 1.769246 H 6.487949 4.554846 0.237941 H 6.903864 2.995552 0.979998 C 4.864999 5.502764 2.230245 H 5.687399 6.026249 2.731751 H 3.982842 5.603592 2.871923 H 4.653174 6.033327 1.294338 C 5.476181 3.310353 3.307575 H 6.322436 3.757503 3.842242 H 5.702336 2.248550 3.153322 H 4.610357 3.368403 3.976115 C -5.416814 -3.306098 -3.239195
C -5.906753 -2.565528 -4.502683 H -5.162531 -2.577369 -5.306400 H -6.134662 -1.516158 -4.280941 H -6.816903 -3.027102 -4.903322 C -5.065972 -4.764192 -3.607555 H -4.303560 -4.822899 -4.391935 H -5.947152 -5.301254 -3.977715 H -4.684256 -5.309838 -2.736433 C -6.606951 -3.360060 -2.254076 H -6.349283 -3.906384 -1.339233 H -7.467719 -3.871152 -2.701974 H -6.941758 -2.355531 -1.970128 N 0.397865 -0.464025 1.326262 H 0.678332 0.006897 2.180249 C 0.156021 -1.834742 1.543804 H -0.592029 -2.296004 0.906179 C 1.407652 -1.304286 0.846197 H 1.485237 -1.523119 -0.209760 C 0.317385 -2.513761 2.893239 C 0.622569 -3.875896 5.360764 C 0.636893 -3.884250 2.946842 C 0.153228 -1.854632 4.122502 C 0.303920 -2.522097 5.342054 C 0.789587 -4.559554 4.161341 H 0.768521 -4.436345 2.018590 H -0.089910 -0.795504 4.135141 H 0.170479 -1.978738 6.273556 H 1.036166 -5.617655 4.167022 H 0.738561 -4.395693 6.307587 C 2.756094 -1.306386 1.489877 H 3.424297 -0.622644 0.958047 H 3.194058 -2.308137 1.440603 H 2.730336 -0.993442 2.538261 Table 4, Bottom, Quadrant II/III C -2.825427 0.690465 2.230397 C -2.348053 2.884532 3.373421 C -4.439696 1.586746 3.955617 C -3.798564 2.966101 3.845911 C -4.293854 0.781744 2.664521 C -2.240556 2.100344 2.062518 H -1.735275 2.409865 4.150363 H -3.971511 1.035027 4.780326 H -4.375247 3.578398 3.141536 H -2.807911 2.648681 1.297272 H -1.963231 3.902421 3.240450 H -5.501292 1.692169 4.206133 H -3.842342 3.472028 4.816957 H -2.286960 0.142530 3.011162 N -2.658601 -0.010707 0.983365 H -4.895464 1.243996 1.871577 N -0.884852 1.976468 1.592490 H -4.704699 -0.220285 2.832941 C -3.444055 -0.876970 0.353730 H -4.381737 -1.180871 0.849574 C -3.200368 -1.461868 -0.972245 C -3.032023 -2.775880 -3.413036
114
C -2.005682 -1.405260 -1.691052 C -4.306506 -2.160409 -1.490766 C -4.254641 -2.821461 -2.720026 C -1.890111 -2.092886 -2.932443 H -5.223485 -2.172267 -0.907194 H -2.984697 -3.300710 -4.363151 C 0.233267 2.602331 1.939236 H 0.215204 3.267041 2.819520 C 1.509228 2.510723 1.221954 C 4.011472 2.653256 0.022658 C 2.585271 3.126488 1.879272 C 1.688441 1.937845 -0.037060 C 2.953702 2.027118 -0.683426 C 3.861038 3.199730 1.306557 H 2.418035 3.556575 2.865125 H 4.988303 2.718466 -0.443358 O -0.905476 -0.745887 -1.243185 O 0.684765 1.295614 -0.695674 Co -0.850071 0.541704 0.107178 Cl -2.024220 1.891147 -1.103723 C 3.203478 1.464364 -2.107269 C 2.254698 2.135459 -3.125552 H 2.394344 3.223185 -3.130642 H 1.198333 1.949309 -2.921513 H 2.445613 1.771234 -4.142046 C 4.636980 1.711443 -2.650123 H 4.870155 2.781323 -2.705748 H 4.750512 1.307090 -3.663641 H 5.396950 1.222986 -2.028939 C 3.012392 -0.065482 -2.110250 H 3.691165 -0.548377 -1.397081 H 3.213338 -0.488911 -3.101316 H 1.999119 -0.362600 -1.839730 C -0.571205 -2.127149 -3.748385 C -0.663194 -2.925625 -5.077038 H 0.295520 -2.916281 -5.610317 H -1.409298 -2.497033 -5.756568 H -0.917909 -3.977595 -4.902331 C -0.149198 -0.699355 -4.152643 H 0.761247 -0.712992 -4.763448 H 0.059859 -0.058706 -3.295790 H -0.935843 -0.208813 -4.738258 C 0.539909 -2.815349 -2.924490 H 1.478451 -2.861910 -3.489324 H 0.255393 -3.842977 -2.667676 H 0.761253 -2.303912 -1.985352 C 5.014524 3.870459 2.074915 C 6.367643 3.845262 1.328159 H 7.155524 4.324209 1.921973 H 6.313467 4.383778 0.374841 H 6.696435 2.819505 1.124151 C 4.666619 5.351406 2.338891 H 5.485841 5.863808 2.856749 H 3.773582 5.462616 2.963600 H 4.479568 5.885796 1.399856 C 5.230621 3.150264 3.424322 H 6.068735 3.590475 3.977268
H 5.453455 2.087764 3.272306 H 4.351826 3.212345 4.075229 C -5.456776 -3.579797 -3.312343 C -5.828975 -2.974386 -4.683592 H -5.019640 -3.072855 -5.415192 H -6.062233 -1.906834 -4.592827 H -6.707398 -3.472615 -5.110313 C -5.092729 -5.069216 -3.495458 H -4.266567 -5.211429 -4.200600 H -5.945179 -5.639640 -3.882595 H -4.793438 -5.521842 -2.542664 C -6.727280 -3.526498 -2.433278 H -6.556691 -3.978389 -1.449174 H -7.553893 -4.075846 -2.899843 H -7.070455 -2.496344 -2.282150 N 0.212704 -0.661871 1.079043 H 1.042926 -0.949689 0.567388 C 0.430614 -0.674159 2.465039 H -0.157334 0.017502 3.057296 C -0.347509 -1.766167 1.733829 H -1.404001 -1.810964 1.961047 C 1.776614 -1.013640 3.079433 C 4.247078 -1.646466 4.313817 C 1.833115 -1.690802 4.311786 C 3.002822 -0.660702 2.493451 C 4.224356 -0.972235 3.097477 C 3.049759 -2.006856 4.923196 H 0.905223 -1.975384 4.804298 H 3.009814 -0.133943 1.544649 H 5.153869 -0.683302 2.614827 H 3.058076 -2.531050 5.874937 H 5.194901 -1.888511 4.786282 C 0.191240 -3.137001 1.491116 H -0.358056 -3.608435 0.669807 H 0.060104 -3.756267 2.383903 H 1.252923 -3.139473 1.225197 Table 4, Bottom, Quadrant III/IV C -2.618603 1.060861 2.315141 C -2.009720 3.175934 3.524986 C -4.309190 2.145583 3.842375 C -3.481547 3.428541 3.856969 C -4.110593 1.330983 2.560768 C -1.885097 2.401942 2.211346 H -1.533761 2.618985 4.341706 H -4.027666 1.529030 4.705308 H -3.899063 4.131674 3.125371 H -2.359782 3.015696 1.432103 H -1.495748 4.141471 3.453072 H -5.370655 2.390539 3.961854 H -3.561412 3.908912 4.838661 H -2.259119 0.488209 3.175374 N -2.365593 0.294411 1.122879 H -4.546558 1.863894 1.706452 N -0.525429 2.183666 1.793038 H -4.665140 0.392441 2.666026 C -3.128361 -0.636482 0.563736
115
H -4.029869 -0.964294 1.108461 C -2.907520 -1.262037 -0.744750 C -2.789813 -2.598752 -3.175351 C -1.778259 -1.107934 -1.546241 C -3.971947 -2.079644 -1.168105 C -3.942552 -2.760881 -2.386919 C -1.692861 -1.791037 -2.793021 H -4.838181 -2.169342 -0.517753 H -2.760329 -3.134111 -4.120203 C 0.613911 2.735075 2.189576 H 0.635830 3.278185 3.149582 C 1.843187 2.765371 1.383781 C 4.235652 3.148015 0.024658 C 2.896005 3.482931 1.972803 C 1.997702 2.200436 0.116094 C 3.199058 2.423160 -0.614978 C 4.119296 3.675923 1.319553 H 2.751013 3.906444 2.964985 H 5.166664 3.312003 -0.506393 O -0.712228 -0.353355 -1.179509 O 1.050314 1.417496 -0.466381 Co -0.549664 0.794838 0.278822 Cl -1.534499 2.323443 -0.886561 C 3.388773 1.935694 -2.077133 C 2.319920 2.582493 -2.986772 H 2.394344 3.676359 -2.960302 H 1.298250 2.325190 -2.698473 H 2.444291 2.265965 -4.029131 C 4.757706 2.313964 -2.704516 H 4.905041 3.399998 -2.733952 H 4.830422 1.956469 -3.739189 H 5.593228 1.865243 -2.154418 C 3.304791 0.399360 -2.158412 H 4.042716 -0.069348 -1.497189 H 3.498140 0.043937 -3.177525 H 2.322970 0.016891 -1.879568 C -0.446613 -1.700457 -3.713240 C -0.595389 -2.451065 -5.064124 H 0.305907 -2.339315 -5.679560 H -1.435499 -2.062120 -5.651508 H -0.743290 -3.527587 -4.918648 C -0.141030 -0.234611 -4.089049 H 0.689450 -0.173156 -4.802549 H 0.148104 0.374121 -3.231991 H -1.013297 0.242388 -4.551245 C 0.764411 -2.341454 -3.003180 H 1.663755 -2.288358 -3.627741 H 0.574819 -3.398636 -2.781395 H 1.003314 -1.856689 -2.054814 C 5.251379 4.456971 2.012297 C 6.548554 4.560328 1.177989 H 7.324734 5.112727 1.721283 H 6.380542 5.090677 0.233387 H 6.959350 3.570519 0.946959 C 4.781663 5.898308 2.305352 H 5.580842 6.487756 2.769841 H 3.925841 5.924835 2.988712
H 4.482107 6.410452 1.383253 C 5.623482 3.763173 3.341368 H 6.454384 4.278549 3.837302 H 5.929296 2.723999 3.171233 H 4.788892 3.748427 4.050733 C -5.097008 -3.657058 -2.871446 C -5.640103 -3.124571 -4.215532 H -4.884741 -3.149631 -5.008478 H -5.981684 -2.087097 -4.119312 H -6.489051 -3.724295 -4.564188 C -4.586896 -5.101724 -3.065029 H -3.808210 -5.168189 -3.832640 H -5.399228 -5.769443 -3.375180 H -4.165537 -5.499023 -2.133952 C -6.292335 -3.724121 -1.893460 H -5.995362 -4.132093 -0.920238 H -7.086700 -4.371456 -2.284219 H -6.735380 -2.734906 -1.729238 N 0.286154 -0.618880 1.192861 H 0.230926 -1.501033 0.689028 C 1.412774 -0.582995 2.035103 H 1.810470 0.377423 2.332136 C 0.026090 -0.855550 2.554083 H -0.333188 -0.071657 3.206722 C 2.459325 -1.675643 1.967673 C 4.457021 -3.677284 1.873735 C 3.021056 -2.206988 3.142049 C 2.943420 -2.171938 0.746627 C 3.926963 -3.162963 0.694614 C 4.005153 -3.198509 3.099695 H 2.681832 -1.839971 4.108604 H 2.537994 -1.777640 -0.180330 H 4.275881 -3.530125 -0.266524 H 4.416932 -3.593514 4.024474 H 5.221493 -4.448502 1.837544 C -0.440783 -2.196949 3.010872 H -1.534879 -2.228524 3.007935 H -0.102202 -2.385293 4.034395 H -0.082102 -3.013213 2.375912 Table 4, Bottom, Quadrant IV/I C -2.142472 0.638030 2.498972 C -1.583455 2.755210 3.740253 C -3.499458 1.297598 4.520294 C -2.945631 2.715225 4.431501 C -3.526540 0.613702 3.154992 C -1.634021 2.078600 2.366126 H -0.834844 2.264256 4.375127 H -2.881534 0.708756 5.209495 H -3.651516 3.345617 3.876487 H -2.320109 2.653461 1.726804 H -1.278653 3.803123 3.638491 H -4.511037 1.321945 4.940906 H -2.861097 3.142202 5.437190 H -1.463411 0.056588 3.134994 N -2.140480 0.064697 1.178914 H -4.261660 1.112231 2.510368
116
N -0.354167 2.051958 1.700713 H -3.866024 -0.420449 3.285810 C -3.026725 -0.688840 0.539686 H -3.963272 -0.948512 1.062079 C -2.881914 -1.212957 -0.824969 C -2.894135 -2.421414 -3.322532 C -1.706522 -1.220320 -1.578801 C -4.057038 -1.794205 -1.334525 C -4.095431 -2.401127 -2.591378 C -1.684789 -1.856143 -2.852294 H -4.952479 -1.760300 -0.719270 H -2.920141 -2.901673 -4.296735 C 0.726087 2.797285 1.896256 H 0.735312 3.492809 2.752305 C 1.920909 2.813298 1.044405 C 4.268071 3.156373 -0.402526 C 2.942562 3.653800 1.516891 C 2.083775 2.111225 -0.148815 C 3.263574 2.303055 -0.925391 C 4.142276 3.833174 0.818888 H 2.792812 4.182935 2.456648 H 5.178846 3.307387 -0.971155 O -0.542788 -0.678262 -1.127118 O 1.161641 1.230377 -0.618459 Co -0.396607 0.613637 0.231038 Cl -1.464492 2.038488 -0.990160 C 3.459061 1.663466 -2.327733 C 2.400170 2.236944 -3.294510 H 2.515929 3.322316 -3.402415 H 1.376211 2.061624 -2.955752 H 2.493070 1.792289 -4.292158 C 4.836254 1.960640 -2.981205 H 4.988423 3.034093 -3.143947 H 4.918873 1.481286 -3.964603 H 5.663090 1.581506 -2.369072 C 3.359754 0.125921 -2.267108 H 4.048952 -0.284700 -1.520138 H 3.608343 -0.327539 -3.234174 H 2.357319 -0.222804 -2.021264 C -0.405889 -1.943107 -3.725620 C -0.592713 -2.718600 -5.057678 H 0.343820 -2.755557 -5.627901 H -1.337070 -2.241049 -5.705673 H -0.900661 -3.756118 -4.882092 C 0.050714 -0.526518 -4.125050 H 0.949502 -0.560477 -4.751768 H 0.287964 0.094312 -3.260955 H -0.731006 -0.005285 -4.690446 C 0.719661 -2.683906 -2.970929 H 1.607632 -2.803019 -3.603175 H 0.392798 -3.684912 -2.665363 H 1.050152 -2.161447 -2.071847 C 5.238086 4.754100 1.386747 C 6.510268 4.833790 0.512329 H 7.261284 5.491385 0.966542 H 6.291734 5.237283 -0.483263 H 6.976828 3.849508 0.388371
C 4.688764 6.190605 1.523858 H 5.460423 6.875060 1.895300 H 3.847053 6.248090 2.222647 H 4.340433 6.573363 0.557205 C 5.676551 4.242584 2.776809 H 6.483584 4.859771 3.188781 H 6.041965 3.210329 2.719564 H 4.857647 4.261571 3.504151 C -5.372163 -3.034391 -3.174275 C -5.739284 -2.335406 -4.501547 H -4.963742 -2.459449 -5.265164 H -5.885174 -1.258885 -4.352791 H -6.667194 -2.743137 -4.919488 C -5.133263 -4.536869 -3.439163 H -4.344909 -4.708126 -4.180203 H -6.040531 -5.020043 -3.820404 H -4.839204 -5.057278 -2.519932 C -6.605272 -2.926398 -2.248185 H -6.438377 -3.436852 -1.292476 H -7.487077 -3.387754 -2.708970 H -6.861890 -1.881520 -2.037982 N 0.364966 -0.688356 1.329978 H -0.314853 -1.352696 1.692599 C 1.562799 -1.355795 0.999900 H 2.187454 -0.920531 0.227788 C 1.398111 -0.493491 2.244310 H 1.952276 0.432465 2.255739 C 1.668003 -2.863329 1.097197 C 1.937092 -5.676877 1.231156 C 2.848535 -3.465893 1.567113 C 0.631029 -3.719626 0.688938 C 0.758860 -5.109401 0.756212 C 2.984041 -4.855114 1.637185 H 3.677706 -2.838079 1.886771 H -0.298593 -3.293346 0.318030 H -0.064837 -5.743632 0.439844 H 3.906573 -5.292316 2.009500 H 2.037923 -6.757294 1.286685 C 1.302874 -1.061022 3.621281 H 0.850240 -0.325338 4.293807 H 2.302296 -1.294055 4.001525 H 0.697761 -1.971923 3.667324 Table 5, Entry a Co -0.304387 0.249231 -0.628782 N -1.426109 1.830435 -0.040976 N -2.003284 -0.219878 -1.630055 C -0.843083 2.897747 0.380231 H -1.493518 3.747635 0.644281 C -2.149834 -1.401314 -2.119096 H -3.087735 -1.597920 -2.663740 C 0.604780 3.106902 0.526695 C 3.260867 3.769913 0.970586 C 1.569710 2.091590 0.527662 C 0.978669 4.443357 0.733998 C 2.313365 4.805932 0.949407 C 2.930587 2.406354 0.778648
117
H 0.223370 5.229134 0.733651 H 4.298045 4.039066 1.151711 C -1.221678 -2.532034 -1.984292 C 0.307678 -4.841106 -1.826978 C -1.777345 -3.778319 -2.314451 C 0.111417 -2.438361 -1.570723 C 0.915749 -3.605853 -1.496052 C -1.030144 -4.959263 -2.235202 H -2.815864 -3.846226 -2.638190 H 0.901075 -5.749958 -1.774370 C -2.878523 1.600997 -0.280733 H -3.210491 0.915866 0.507137 C -2.970687 0.922181 -1.665525 H -2.610331 1.594439 -2.456316 O 1.251601 0.768781 0.374966 O 0.715090 -1.242756 -1.293132 C -4.414510 0.519985 -1.954285 H -4.504123 0.078323 -2.953686 H -4.757734 -0.236255 -1.236354 C -3.742828 2.856143 -0.242220 H -3.382880 3.600155 -0.964499 H -3.706197 3.323993 0.748841 C -5.197449 2.501428 -0.561870 H -5.799245 3.416494 -0.599220 H -5.604957 1.885832 0.249907 C -5.333624 1.743278 -1.882203 H -6.374395 1.428757 -2.019582 H -5.094871 2.421281 -2.711196 C 4.044912 1.325783 0.863642 C 2.413658 -3.573367 -1.081643 C 3.746950 0.346230 2.020946 H 4.540809 -0.404002 2.116864 H 2.811815 -0.202988 1.892364 H 3.676995 0.880369 2.976186 C 4.153944 0.566688 -0.474371 H 4.957744 -0.178327 -0.443660 H 4.368504 1.255087 -1.300431 H 3.240056 0.030851 -0.731315 C 2.568886 -2.968699 0.330077 H 1.979044 -3.529854 1.064626 H 2.247750 -1.928482 0.385422 H 3.615240 -2.988823 0.657184 C 3.226202 -2.762449 -2.114222 H 3.148680 -3.211725 -3.111688 H 4.288572 -2.732419 -1.844914 H 2.893067 -1.726491 -2.205768 C 3.090632 -4.968741 -1.012234 H 3.088323 -5.471188 -1.986656 H 2.596593 -5.622473 -0.283791 H 4.140182 -4.883407 -0.704380 C 5.464324 1.888162 1.143953 H 6.206289 1.081424 1.191525 H 5.509365 2.416841 2.103368 H 5.791985 2.574320 0.354111 N -0.898409 -0.826427 0.993818 C -1.477211 -1.969632 1.569356 C -0.901179 -0.865761 2.422268
H -0.900652 -2.890466 1.528973 H 0.053533 -1.125584 2.882809 C -2.922776 -2.236930 1.366989 H -3.488299 -1.342224 1.095328 H -3.359323 -2.672253 2.270919 H -3.058607 -2.962378 0.558592 C -1.602711 0.310049 3.058903 C -2.790614 2.610548 4.224851 C -2.964258 0.343316 3.397042 C -0.847403 1.454217 3.392737 C -1.428124 2.592994 3.957520 C -3.556740 1.481531 3.956689 H -3.590838 -0.534890 3.271818 H 0.232688 1.444524 3.246779 H -0.810105 3.446079 4.232764 H -4.611380 1.468572 4.229020 H -3.245621 3.478550 4.699440 Cl 0.303604 1.388879 -2.358008 C -1.675600 -6.315142 -2.594776 C -0.726431 -7.526565 -2.451150 H -0.364706 -7.636227 -1.422111 H 0.143063 -7.439158 -3.113041 H -1.236540 -8.461244 -2.713735 C -2.883428 -6.573456 -1.667392 H -2.579743 -6.566360 -0.613794 H -3.341019 -7.547559 -1.876303 H -3.668912 -5.819499 -1.787925 C -2.156922 -6.286266 -4.061703 H -1.326269 -6.072357 -4.744724 H -2.926383 -5.525329 -4.231592 H -2.590092 -7.249843 -4.354609 C 2.692336 6.286901 1.167776 C 1.970127 6.823697 2.422717 H 2.230138 6.233673 3.309606 H 0.880014 6.796251 2.318074 H 2.246333 7.865685 2.622343 C 2.263541 7.118349 -0.061147 H 2.733454 6.739397 -0.976485 H 2.553402 8.169586 0.052136 H 1.179410 7.101728 -0.216911 C 4.204825 6.530074 1.373570 H 4.788423 6.197976 0.507017 H 4.581054 6.008092 2.261116 H 4.417658 7.596573 1.515248 Table 5, Entry b Co -0.099005 0.460758 -0.545746 N -1.279295 2.032916 -0.051708 N -1.688634 0.015639 -1.730248 C -0.749567 3.076575 0.484075 H -1.428283 3.915311 0.710061 C -1.796239 -1.162194 -2.236909 H -2.671877 -1.344585 -2.881190 C 0.673064 3.281943 0.793850 C 3.272216 3.947676 1.501578 C 1.646613 2.276449 0.837226 C 1.011826 4.611006 1.093337
118
C 2.317469 4.975099 1.443371 C 2.977252 2.591934 1.218933 H 0.251920 5.391597 1.057050 H 4.285838 4.217060 1.786004 C -0.903173 -2.305602 -2.002856 C 0.572871 -4.623732 -1.677703 C -1.440252 -3.546824 -2.386670 C 0.382775 -2.223148 -1.455956 C 1.162252 -3.396941 -1.294289 C -0.720814 -4.731382 -2.222377 H -2.438866 -3.588603 -2.816513 H 1.135787 -5.549209 -1.564898 C -2.696972 1.826061 -0.475563 H -3.131186 1.138006 0.256798 C -2.621753 1.174493 -1.872718 H -2.144000 1.853577 -2.592548 O 1.363155 0.959297 0.598490 O 0.969473 -1.029723 -1.135138 C -4.016622 0.815440 -2.373874 H -3.971136 0.402263 -3.388452 H -4.474700 0.050214 -1.737507 C -3.540931 3.095371 -0.525463 H -3.075484 3.848085 -1.174833 H -3.631369 3.541469 0.472111 C -4.944871 2.775079 -1.045709 H -5.523087 3.701541 -1.136422 H -5.466100 2.145073 -0.314036 C -4.913223 2.056432 -2.394120 H -5.930968 1.769154 -2.681620 H -4.549973 2.750355 -3.162471 C 4.095063 1.519130 1.350664 C 2.611179 -3.381258 -0.735026 C 3.722267 0.503614 2.453327 H 4.508143 -0.250848 2.577089 H 2.796756 -0.037187 2.245365 H 3.589055 1.006641 3.418692 C 4.312623 0.800514 0.002904 H 5.130237 0.072914 0.068792 H 4.566518 1.516706 -0.787568 H 3.433043 0.249721 -0.330773 C 2.634322 -2.769073 0.681188 H 1.963690 -3.313884 1.356290 H 2.327662 -1.723204 0.695303 H 3.641921 -2.803742 1.112171 C 3.533068 -2.586420 -1.684924 H 3.544599 -3.036290 -2.685034 H 4.564842 -2.573449 -1.314290 H 3.227902 -1.544984 -1.807620 C 3.257301 -4.785457 -0.592918 H 3.343065 -5.293618 -1.560587 H 2.684268 -5.427683 0.086243 H 4.272619 -4.713335 -0.183654 C 5.484117 2.085194 1.750739 H 6.231094 1.284815 1.821668 H 5.455783 2.577900 2.729730 H 5.856865 2.803804 1.011347 N -0.848787 -0.616886 1.000479
C -1.616140 -1.587817 1.714826 C -0.610408 -0.685433 2.384480 H -1.277719 -2.619805 1.610642 H 0.316892 -1.155284 2.702282 C -0.924621 0.493589 3.230806 H -1.693934 1.138174 2.797463 H -0.026000 1.104844 3.364278 H -1.251707 0.171430 4.224007 C -3.109323 -1.398544 1.594516 C -5.915193 -1.119274 1.251894 C -3.802707 -2.044447 0.550291 C -3.892964 -0.662258 2.497304 C -5.272985 -0.507368 2.321847 C -5.182291 -1.905843 0.372998 H -3.266182 -2.725045 -0.106499 H -3.452712 -0.224800 3.388841 H -5.854957 0.055066 3.050813 H -5.694525 -2.447013 -0.420359 H -6.994726 -1.030782 1.141063 C -1.279267 -6.115814 -2.616241 C -1.313353 -7.034662 -1.375373 H -0.313951 -7.220301 -0.967268 H -1.744835 -8.012487 -1.619530 H -1.918817 -6.593189 -0.574832 C -0.379175 -6.751138 -3.697885 H 0.640651 -6.927534 -3.339095 H -0.309785 -6.105825 -4.581624 H -0.775831 -7.720197 -4.022672 C -2.715441 -6.071694 -3.186507 H -2.768742 -5.468589 -4.100380 H -3.425130 -5.657423 -2.460809 H -3.069048 -7.077212 -3.444639 C 2.657965 6.448186 1.758119 C 2.335691 7.327812 0.530177 H 2.892955 6.991680 -0.352288 H 2.601638 8.375460 0.713630 H 1.270983 7.309450 0.273366 C 1.816972 6.926553 2.961604 H 2.000025 6.301338 3.843573 H 0.741616 6.896444 2.754972 H 2.062434 7.960998 3.229139 C 4.142098 6.693362 2.113813 H 4.807168 6.404604 1.291566 H 4.440662 6.135230 3.008858 H 4.328562 7.754102 2.320834 Cl 0.682812 1.623894 -2.186947 Table 5, Entry c Co 0.269768 0.032347 -0.607828 N -0.833505 1.616183 -0.013996 N -1.435805 -0.454522 -1.558119 C -0.245218 2.667309 0.441928 H -0.889936 3.503449 0.761475 C -1.582450 -1.637106 -2.046899 H -2.521772 -1.841547 -2.587754 C 1.201265 2.889213 0.551989 C 3.871630 3.560393 0.914494
119
C 2.176077 1.882562 0.502550 C 1.566497 4.224814 0.767518 C 2.904090 4.570667 0.926245 C 3.546052 2.201316 0.713724 H 0.819870 5.017998 0.815807 H 4.903174 3.872090 1.077482 C -0.649982 -2.763946 -1.926699 C 0.910195 -5.059485 -1.803860 C -1.205825 -4.010216 -2.247936 C 0.693584 -2.662305 -1.540254 C 1.513722 -3.823629 -1.484781 C -0.435832 -5.165634 -2.168898 H -2.245940 -4.105675 -2.560918 H 1.484642 -5.985459 -1.786284 C -2.303454 1.445955 -0.269178 H -2.655274 0.813543 0.554707 C -2.422282 0.678418 -1.621881 H -2.046695 1.312199 -2.436639 O 1.858660 0.560960 0.344361 O 1.291963 -1.460055 -1.277596 C 4.668680 1.129387 0.750841 C 3.019742 -3.779462 -1.109935 C 4.419778 0.143096 1.913409 H 5.216637 -0.607813 1.971034 H 3.478834 -0.403562 1.821127 H 4.390463 0.671255 2.874094 C 4.734258 0.377430 -0.593742 H 5.545273 -0.360356 -0.596715 H 4.911434 1.071263 -1.424100 H 3.816236 -0.165643 -0.818435 C 3.208791 -3.166956 0.293868 H 2.642603 -3.727976 1.046879 H 2.882184 -2.128665 0.352079 H 4.263648 -3.178632 0.592830 C 3.799095 -2.968955 -2.167602 H 3.701959 -3.426286 -3.159687 H 4.867280 -2.926689 -1.924330 H 3.452505 -1.937330 -2.258660 C 3.703336 -5.171843 -1.052063 H 3.679905 -5.677517 -2.024497 H 3.228153 -5.825126 -0.310808 H 4.759453 -5.081642 -0.769164 C 6.091947 1.704006 0.980951 H 6.843235 0.904650 0.992745 H 6.168930 2.225140 1.942425 H 6.380974 2.400913 0.185479 N -0.248213 -1.032753 1.047192 C -0.770820 -2.197525 1.634352 C -0.214822 -1.075251 2.475298 H -0.163905 -3.097375 1.575018 H 0.760808 -1.296387 2.911221 C -2.210805 -2.512803 1.473018 H -2.814227 -1.624355 1.278369 H -2.593734 -3.011889 2.368249 H -2.355302 -3.196989 0.631530 C -0.958240 0.054779 3.144902 C -2.231189 2.260004 4.400858
C -2.291098 -0.014517 3.578951 C -0.269705 1.252180 3.429641 C -0.894294 2.345654 4.035551 C -2.925878 1.074836 4.186798 H -2.855073 -0.939632 3.499579 H 0.796750 1.320218 3.217216 H -0.326383 3.244780 4.268562 H -3.953705 0.981868 4.535257 H -2.716048 3.093443 4.906738 Cl 0.820254 1.161501 -2.362584 C -1.015246 -6.503055 -2.538745 C 3.304446 5.997346 1.182146 C -3.834746 0.238959 -1.969872 C -6.413158 -0.596060 -2.718446 C -4.307980 0.442910 -3.280029 C -4.683999 -0.389260 -1.042041 C -5.963522 -0.802301 -1.418087 C -5.587708 0.027234 -3.648053 H -3.702306 0.935103 -4.041197 H -4.396355 -0.570839 -0.010073 H -6.624697 -1.280329 -0.695811 H -5.951930 0.196083 -4.661058 H -7.415328 -0.911706 -3.006181 C -3.077317 2.754654 -0.261431 C -4.511046 5.168930 -0.149436 C -3.943918 3.028163 0.811590 C -2.942793 3.718158 -1.279369 C -3.657950 4.915354 -1.219141 C -4.654266 4.227249 0.864363 H -4.091959 2.318358 1.624773 H -2.289120 3.580092 -2.138466 H -3.559748 5.658585 -2.009958 H -5.329807 4.430558 1.694515 H -5.072815 6.101379 -0.108793 H -0.562670 -7.301957 -1.942009 H -0.837934 -6.706246 -3.599275 H -2.093489 -6.528109 -2.349101 H 4.287522 6.209623 0.748955 H 2.591857 6.691599 0.724515 H 3.341057 6.187211 2.259217 Table 5, Entry d Co 0.300379 0.065815 -0.610639 N -0.832032 1.640597 -0.084300 N -1.310343 -0.392918 -1.710409 C -0.312626 2.617026 0.574369 H -1.000490 3.416407 0.900767 C -1.436093 -1.577971 -2.199640 H -2.322450 -1.768909 -2.828548 C 1.105920 2.817919 0.881612 C 3.728160 3.475824 1.515473 C 2.099603 1.834347 0.793819 C 1.425982 4.121588 1.286030 C 2.739406 4.461820 1.589301 C 3.448842 2.148934 1.120407 H 0.662795 4.896389 1.365941 H 4.738987 3.779918 1.786416
120
C -0.542555 -2.720612 -1.983123 C 0.988157 -5.027073 -1.769401 C -1.099643 -3.964597 -2.307921 C 0.781086 -2.627246 -1.533154 C 1.592754 -3.792287 -1.447556 C -0.346138 -5.126357 -2.178438 H -2.125089 -4.052362 -2.667767 H 1.553239 -5.957785 -1.721551 C -2.255306 1.563937 -0.552124 H -2.777253 1.020640 0.240623 C -2.276533 0.742292 -1.872263 H -1.857829 1.332607 -2.697810 O 1.814787 0.531594 0.489993 O 1.366513 -1.427517 -1.232807 C 4.601220 1.108578 1.073984 C 3.092325 -3.753580 -1.046669 C 4.362581 0.017312 2.137289 H 5.174021 -0.719883 2.137449 H 3.434445 -0.532811 1.976328 H 4.307846 0.453001 3.142115 C 4.709007 0.480197 -0.331392 H 5.556576 -0.212842 -0.392116 H 4.853749 1.251750 -1.096848 H 3.823303 -0.090985 -0.610041 C 3.252815 -3.178840 0.374378 H 2.694292 -3.775672 1.104975 H 2.896604 -2.151930 0.455163 H 4.304519 -3.172642 0.684074 C 3.890261 -2.909582 -2.064722 H 3.795854 -3.324498 -3.075467 H 4.956939 -2.890468 -1.811634 H 3.560046 -1.869761 -2.113761 C 3.781111 -5.144125 -1.018007 H 3.763504 -5.626338 -2.002436 H 3.305758 -5.816871 -0.294504 H 4.835153 -5.056688 -0.726624 C 6.005557 1.697923 1.374281 H 6.781389 0.925423 1.304163 H 6.065568 2.111505 2.387789 H 6.273486 2.486848 0.661657 N -0.449704 -1.027090 0.930066 C -1.496646 -1.498144 1.765698 C -0.070183 -1.951884 1.928277 H -2.137017 -2.259938 1.319833 H 0.155132 -2.964856 1.607935 C 0.797821 -1.539787 3.061805 H 1.141261 -0.506552 2.976951 H 1.693047 -2.169946 3.091597 H 0.278272 -1.665409 4.016621 C -2.225037 -0.436012 2.561531 C -3.736858 1.544209 3.931108 C -3.623237 -0.536791 2.714056 C -1.617799 0.691009 3.146412 C -2.357860 1.669104 3.819814 C -4.371246 0.437082 3.382556 H -4.154166 -1.405890 2.325441 H -0.541015 0.818432 3.111384
H -1.855262 2.511701 4.291923 H -5.446843 0.314894 3.502190 H -4.313241 2.287626 4.479503 C -0.924966 -6.463755 -2.549464 C 3.088486 5.849460 2.051417 Cl 1.036840 1.242311 -2.261939 C -2.902706 2.930101 -0.728722 C -4.131114 5.442601 -0.977766 C -3.992299 3.280272 0.087832 C -2.440430 3.863896 -1.676179 C -3.054449 5.111296 -1.795203 C -4.599892 4.529075 -0.038587 H -4.396523 2.593683 0.832030 H -1.601891 3.660700 -2.340327 H -2.701520 5.834020 -2.530407 H -5.448441 4.793870 0.591377 H -4.612613 6.414765 -1.077157 C -3.683542 0.295538 -2.241648 C -6.265673 -0.513324 -2.995466 C -4.210574 0.653528 -3.494673 C -4.479436 -0.473052 -1.370209 C -5.761185 -0.873123 -1.749541 C -5.493044 0.249438 -3.865809 H -3.648013 1.259844 -4.204778 H -4.136644 -0.781044 -0.384936 H -6.380648 -1.462773 -1.074628 H -5.900841 0.535767 -4.834951 H -7.269316 -0.820204 -3.287775 H -0.712547 -6.684044 -3.600087 H -0.501256 -7.257910 -1.925807 H -2.009374 -6.476060 -2.397452 H 4.091683 6.131125 1.714623 H 2.390076 6.586229 1.640824 H 3.052280 5.898966 3.143985 Table 5, Entry e Co -0.172498 0.226796 -0.638552 N -1.325026 1.904067 -0.155040 N -1.911362 -0.253110 -1.668075 C -0.722885 2.938178 0.318454 H -1.358423 3.806569 0.557239 C -2.069387 -1.460487 -2.085922 H -3.006885 -1.676286 -2.623860 C 0.723324 3.100029 0.538336 C 3.374362 3.722268 1.087879 C 1.678273 2.073470 0.546076 C 1.109444 4.426047 0.795814 C 2.439343 4.767995 1.067406 C 3.035895 2.369223 0.844885 H 0.366319 5.223644 0.789312 H 4.407881 3.974541 1.309176 C -1.142615 -2.586632 -1.910201 C 0.396083 -4.889174 -1.729590 C -1.708117 -3.844621 -2.172946 C 0.204873 -2.478967 -1.548274 C 1.015740 -3.642463 -1.471939 C -0.957756 -5.022312 -2.075491
121
H -2.757562 -3.924162 -2.456411 H 0.992298 -5.795546 -1.667396 C -2.790565 1.751795 -0.510027 C -2.842767 0.931460 -1.851090 O 1.368201 0.754025 0.355754 O 0.816169 -1.277960 -1.315078 C -4.307738 0.530196 -2.119796 H -4.397731 -0.014187 -3.068926 H -4.676589 -0.159602 -1.351217 C -3.528286 3.085281 -0.741437 H -3.032298 3.687227 -1.512202 H -3.522859 3.704241 0.164978 C -4.998188 2.849564 -1.139732 H -5.429231 3.793839 -1.494425 H -5.572591 2.593083 -0.241156 C -5.237051 1.758849 -2.194322 H -6.279338 1.422051 -2.133418 H -5.145389 2.215086 -3.187284 C 4.139972 1.276106 0.927235 C 2.531528 -3.593505 -1.128032 C 3.811098 0.275330 2.057359 H 4.595993 -0.484358 2.152354 H 2.873675 -0.261564 1.899068 H 3.727381 0.789618 3.022328 C 4.272041 0.544746 -0.425007 H 5.073511 -0.202877 -0.394817 H 4.504408 1.250235 -1.231607 H 3.363255 0.015492 -0.712430 C 2.741261 -2.992203 0.277276 H 2.210409 -3.576838 1.037916 H 2.386334 -1.964425 0.355889 H 3.803491 -2.979420 0.548609 C 3.291909 -2.769081 -2.190392 H 3.155892 -3.199936 -3.189644 H 4.367873 -2.751108 -1.979949 H 2.966340 -1.728081 -2.243535 C 3.227060 -4.981134 -1.097411 H 3.171796 -5.484451 -2.069844 H 2.785327 -5.639701 -0.340309 H 4.291649 -4.883785 -0.850851 C 5.558594 1.819677 1.247644 H 6.293434 1.006015 1.287624 H 5.590713 2.322453 2.221395 H 5.905487 2.523546 0.481960 N -0.620159 -0.918846 1.054668 C -1.028134 -2.133352 1.642141 C -0.485578 -1.003651 2.477422 H -0.362771 -2.982704 1.506332 H 0.531666 -1.171316 2.834024 C -2.440463 -2.582494 1.610429 H -3.171467 -1.776962 1.656353 H -2.632597 -3.256861 2.451382 H -2.635260 -3.146531 0.693762 C -1.254322 0.019864 3.270753 C -2.585255 2.008845 4.796085 C -2.461757 -0.248387 3.934763 C -0.707347 1.305334 3.459700
C -1.363055 2.292855 4.199948 C -3.129254 0.734694 4.674077 H -2.892167 -1.246565 3.918879 H 0.285456 1.523562 3.074269 H -0.899062 3.264473 4.356632 H -4.058357 0.491812 5.187391 H -3.089655 2.759759 5.401530 Cl 0.595431 1.303491 -2.342778 C -1.616793 -6.390809 -2.353015 C -0.663465 -7.596986 -2.193738 H -0.261840 -7.662360 -1.175788 H 0.179533 -7.540657 -2.892262 H -1.183985 -8.541047 -2.395213 C -2.788832 -6.607201 -1.370488 H -2.445607 -6.555404 -0.330346 H -3.254013 -7.588600 -1.520046 H -3.578345 -5.857871 -1.493507 C -2.153070 -6.422901 -3.800608 H -1.348643 -6.239918 -4.522875 H -2.927852 -5.668048 -3.973437 H -2.597598 -7.397029 -4.035917 C 2.825977 6.237836 1.340719 C 2.062505 6.749541 2.581697 H 2.281508 6.132431 3.461196 H 0.976957 6.738953 2.435116 H 2.342983 7.782146 2.820338 C 2.453730 7.107133 0.119620 H 2.954362 6.747494 -0.787185 H 2.750343 8.151425 0.272657 H 1.376274 7.107443 -0.077790 C 4.332073 6.457118 1.610614 H 4.944775 6.143811 0.757253 H 4.668579 5.904893 2.495811 H 4.550693 7.516456 1.791722 C -3.438370 1.064700 0.709264 H -2.979301 0.104135 0.910755 H -4.507463 0.871843 0.590733 H -3.330548 1.683109 1.607375 C -2.323664 1.697355 -3.101781 H -1.438912 2.300273 -2.892229 H -3.052871 2.408518 -3.499073 H -2.080516 1.010436 -3.921665 Table 5, Entry f Co 0.018066 0.444131 -0.517170 N -1.152469 2.130283 -0.138080 N -1.604974 0.006386 -1.740437 C -0.597169 3.139698 0.435525 H -1.247603 4.008545 0.628482 C -1.718364 -1.182838 -2.219339 H -2.582309 -1.365099 -2.878995 C 0.816536 3.278939 0.819674 C 3.406885 3.874628 1.628940 C 1.764857 2.248639 0.883737 C 1.178700 4.594461 1.157202 C 2.477512 4.922867 1.562384 C 3.092561 2.531919 1.307220
122
H 0.441318 5.395860 1.106507 H 4.416199 4.116427 1.950553 C -0.837682 -2.330698 -1.963772 C 0.611767 -4.664800 -1.621373 C -1.381542 -3.568473 -2.352449 C 0.444551 -2.260148 -1.407440 C 1.210941 -3.442693 -1.238508 C -0.677769 -4.760543 -2.176420 H -2.376587 -3.601985 -2.791462 H 1.163369 -5.595871 -1.499691 C -2.574503 2.009913 -0.652281 C -2.496860 1.206100 -2.001601 O 1.472439 0.936772 0.624738 O 1.046635 -1.076284 -1.082876 C -3.931493 0.829958 -2.424852 H -3.931574 0.296061 -3.384017 H -4.387987 0.138978 -1.705931 C -3.258896 3.359727 -0.944833 H -2.671568 3.960795 -1.649178 H -3.341106 3.968846 -0.035545 C -4.681463 3.156210 -1.502325 H -5.052061 4.110824 -1.895609 H -5.355145 2.909017 -0.672697 C -4.828939 2.074438 -2.583003 H -5.877230 1.754539 -2.630721 H -4.629813 2.534499 -3.558379 C 4.191569 1.438080 1.439382 C 2.658161 -3.440947 -0.672928 C 3.789421 0.418364 2.526336 H 4.561781 -0.349364 2.653325 H 2.859661 -0.105162 2.297779 H 3.649414 0.913276 3.494866 C 4.414825 0.729332 0.086732 H 5.225933 -0.005535 0.153166 H 4.681485 1.450389 -0.695037 H 3.534836 0.187102 -0.259618 C 2.682661 -2.829174 0.743198 H 2.005166 -3.367708 1.416344 H 2.386059 -1.780480 0.755858 H 3.688560 -2.873209 1.177287 C 3.592078 -2.655218 -1.618962 H 3.600472 -3.102904 -2.620069 H 4.623062 -2.655791 -1.245862 H 3.300576 -1.609620 -1.739629 C 3.290295 -4.851378 -0.528559 H 3.373822 -5.360645 -1.495846 H 2.709310 -5.487752 0.149355 H 4.305108 -4.789011 -0.116431 C 5.586057 1.975796 1.860551 H 6.320147 1.162921 1.923887 H 5.557749 2.451224 2.848043 H 5.975582 2.701340 1.136730 N -0.634917 -0.701857 1.108619 C -1.216024 -1.757023 1.888454 C -0.392053 -0.652243 2.495215 H -0.697793 -2.713701 1.813283 H 0.602707 -0.930789 2.831461
C -0.913690 0.494962 3.279914 H -1.857645 0.884815 2.896285 H -0.189357 1.315456 3.267702 H -1.057656 0.203110 4.324711 C -2.718329 -1.868355 1.911852 C -5.543383 -2.141885 1.883101 C -3.395692 -2.490865 0.845116 C -3.510458 -1.453109 2.995485 C -4.904460 -1.570561 2.977614 C -4.787403 -2.618039 0.819359 H -2.823131 -2.938781 0.040781 H -3.049796 -1.052184 3.895008 H -5.489054 -1.245630 3.836741 H -5.280951 -3.127504 -0.005320 H -6.625341 -2.260229 1.885511 C -1.249673 -6.140344 -2.566573 C -1.306489 -7.050023 -1.319759 H -0.313207 -7.245091 -0.901228 H -1.747863 -8.024114 -1.561120 H -1.913667 -6.595444 -0.527855 C -0.347909 -6.794136 -3.635685 H 0.666306 -6.980968 -3.266439 H -0.262366 -6.155661 -4.522966 H -0.753807 -7.760283 -3.957716 C -2.680062 -6.082338 -3.149983 H -2.717809 -5.484405 -4.068019 H -3.391091 -5.654913 -2.433252 H -3.043636 -7.085087 -3.405013 C 2.838039 6.381278 1.919811 C 2.587416 7.290781 0.697003 H 3.173574 6.958284 -0.167947 H 2.868826 8.328380 0.911798 H 1.534286 7.301740 0.395832 C 1.958886 6.857195 3.096821 H 2.090213 6.211194 3.973012 H 0.892678 6.857332 2.845499 H 2.217193 7.880144 3.394761 C 4.311160 6.584671 2.341635 H 5.003440 6.298910 1.541086 H 4.559851 6.000343 3.235215 H 4.512130 7.636137 2.580016 Cl 0.980029 1.531278 -2.112582 C -3.363155 1.324517 0.482521 H -2.954221 0.347363 0.704239 H -4.419984 1.166654 0.253456 H -3.327225 1.917976 1.404010 C -1.839777 1.979140 -3.181284 H -0.969295 2.560426 -2.873776 H -2.511645 2.710315 -3.638806 H -1.527742 1.299204 -3.983486 Table 5, Entry g Co -0.306163 0.246396 -0.641354 N -1.428110 1.830101 -0.062536 N -2.004529 -0.225958 -1.646186 C -0.845748 2.899346 0.354837 H -1.496561 3.751576 0.610709
123
C -2.149017 -1.408105 -2.134182 H -3.084762 -1.605496 -2.682321 C 0.601317 3.107600 0.509164 C 3.254325 3.770071 0.971703 C 1.566523 2.092443 0.513097 C 0.973427 4.443464 0.723395 C 2.306448 4.805639 0.949117 C 2.925922 2.407151 0.772317 H 0.218295 5.229603 0.721060 H 4.290281 4.039251 1.159962 C -1.221619 -2.538623 -1.993196 C 0.306296 -4.847810 -1.824233 C -1.776764 -3.785636 -2.321413 C 0.110169 -2.444291 -1.575546 C 0.913831 -3.611854 -1.495030 C -1.030281 -4.966623 -2.236317 H -2.814137 -3.854189 -2.648771 H 0.899234 -5.756753 -1.767518 C -2.880386 1.600391 -0.304647 H -3.212505 0.919318 0.487220 C -2.971344 0.916477 -1.687163 H -2.609873 1.585653 -2.480016 O 1.250670 0.769460 0.357219 O 0.713616 -1.248362 -1.299141 C -4.415008 0.513496 -1.975390 H -4.504067 0.068174 -2.973208 H -4.758791 -0.240086 -1.254927 C -3.744567 2.855778 -0.270765 H -3.383896 3.597519 -0.995000 H -3.708773 3.326530 0.719042 C -5.198903 2.500104 -0.590625 H -5.800551 3.415105 -0.631767 H -5.607281 1.887438 0.222930 C -5.333942 1.737254 -1.908399 H -6.374647 1.422438 -2.045611 H -5.094318 2.412280 -2.739566 C 4.040683 1.327023 0.859362 C 2.410656 -3.578792 -1.076551 C 3.739941 0.347521 2.015938 H 4.532802 -0.403625 2.112831 H 2.804184 -0.200301 1.885826 H 3.669126 0.881479 2.971224 C 4.153561 0.567757 -0.478345 H 4.959121 -0.175309 -0.446163 H 4.367792 1.256458 -1.304231 H 3.241610 0.029257 -0.736630 C 2.562207 -2.969997 0.333795 H 1.969343 -3.528099 1.068234 H 2.242304 -1.929174 0.384795 H 3.607503 -2.990391 0.664255 C 3.226417 -2.771072 -2.109104 H 3.151210 -3.222860 -3.105609 H 4.288097 -2.741009 -1.837088 H 2.894200 -1.735119 -2.204105 C 3.086839 -4.974223 -1.001208 H 3.087083 -5.479466 -1.974186 H 2.590462 -5.625642 -0.272283
H 4.135552 -4.888445 -0.690639 C 5.459224 1.889957 1.142934 H 6.201696 1.083678 1.190371 H 5.502500 2.416889 2.103388 H 5.787478 2.577816 0.354819 N -0.897426 -0.828187 0.990631 C -1.488393 -1.971394 1.554071 C -0.886102 -0.891012 2.418629 H -0.927176 -2.900614 1.492962 H 0.069799 -1.171798 2.864290 C -2.940281 -2.212543 1.363807 H -3.496982 -1.302588 1.127343 H -3.370548 -2.668283 2.260673 H -3.097400 -2.911632 0.536294 C -1.565098 0.283687 3.080902 C -2.718111 2.587055 4.264392 C -2.918112 0.318581 3.454567 C -0.796597 1.424183 3.397922 C -1.361261 2.567771 3.971084 C -3.496340 1.461166 4.023169 H -3.549974 -0.558094 3.341112 H 0.279340 1.411580 3.223147 H -0.733813 3.423595 4.213419 H -4.548637 1.453118 4.303276 Cl 0.301943 1.380227 -2.374067 C -1.674948 -6.323300 -2.594542 C -0.726885 -7.534719 -2.443756 H -0.369000 -7.641414 -1.413064 H 0.145077 -7.449737 -3.102709 H -1.236462 -8.469952 -2.705399 C -2.886494 -6.578497 -1.671149 H -2.586919 -6.568510 -0.616399 H -3.343649 -7.553019 -1.879061 H -3.671217 -5.824605 -1.796907 C -2.150533 -6.298348 -4.063405 H -1.317121 -6.086770 -4.743785 H -2.918945 -5.537514 -4.238434 H -2.583030 -7.262542 -4.355269 C 2.683076 6.285941 1.176729 C 1.951724 6.816664 2.429004 H 2.205723 6.222680 3.314996 H 0.862383 6.789236 2.316572 H 2.226024 7.857843 2.635352 C 2.262504 7.122657 -0.051434 H 2.739057 6.748043 -0.965123 H 2.551002 8.173519 0.068599 H 1.179509 7.106191 -0.214914 C 4.193931 6.528915 1.394344 H 4.783813 6.201270 0.530357 H 4.564172 6.002887 2.282021 H 4.405167 7.594838 1.542590 Cl -3.432192 4.002845 4.918586 Table 5, Entry h Co -0.095960 0.464042 -0.535947 N -1.271511 2.039009 -0.046600 N -1.682780 0.023023 -1.727675
124
C -0.738457 3.086177 0.479259 H -1.414587 3.928738 0.698918 C -1.783612 -1.149510 -2.247857 H -2.652741 -1.326109 -2.902554 C 0.685195 3.289327 0.786617 C 3.286276 3.950459 1.490937 C 1.654850 2.280184 0.839397 C 1.028878 4.619517 1.074813 C 2.335720 4.981239 1.422794 C 2.986270 2.593461 1.219823 H 0.272224 5.402908 1.031152 H 4.300752 4.218383 1.773816 C -0.893724 -2.295167 -2.013856 C 0.571975 -4.618871 -1.682690 C -1.428825 -3.532818 -2.411985 C 0.385530 -2.218887 -1.450804 C 1.159454 -3.395755 -1.284854 C -0.714532 -4.720095 -2.245203 H -2.421541 -3.569932 -2.855807 H 1.131282 -5.546399 -1.568337 C -2.690163 1.828670 -0.463557 H -3.117200 1.135418 0.269395 C -2.620518 1.180200 -1.863097 H -2.150224 1.861944 -2.585189 O 1.366002 0.962164 0.610666 O 0.972475 -1.028719 -1.119001 C -4.018316 0.814189 -2.352200 H -3.980064 0.403861 -3.368192 H -4.465489 0.044339 -1.713314 C -3.540817 3.093376 -0.503405 H -3.085720 3.849468 -1.156136 H -3.624236 3.537481 0.495674 C -4.947534 2.765041 -1.011027 H -5.532580 3.687869 -1.094575 H -5.457926 2.130114 -0.275890 C -4.923363 2.049237 -2.361118 H -5.941800 1.755654 -2.639706 H -4.571958 2.747164 -3.131341 C 4.099956 1.517638 1.361267 C 2.601522 -3.387154 -0.707758 C 3.721202 0.509843 2.468992 H 4.505339 -0.245106 2.600640 H 2.795847 -0.031069 2.260721 H 3.585059 1.019252 3.430582 C 4.317835 0.790201 0.018415 H 5.131879 0.059230 0.090735 H 4.577051 1.500517 -0.775623 H 3.436347 0.241778 -0.314125 C 2.611993 -2.773354 0.708051 H 1.927755 -3.311163 1.375054 H 2.315492 -1.724518 0.717331 H 3.613599 -2.816757 1.152053 C 3.538103 -2.598410 -1.648143 H 3.561693 -3.051975 -2.646381 H 4.564878 -2.586787 -1.263888 H 3.236756 -1.556837 -1.778986 C 3.238258 -4.794646 -0.556089
H 3.335423 -5.303671 -1.522217 H 2.652066 -5.433572 0.114907 H 4.248065 -4.727655 -0.132567 C 5.489974 2.081268 1.761332 H 6.233736 1.278618 1.839966 H 5.460601 2.580996 2.736728 H 5.867640 2.793200 1.017988 N -0.850601 -0.619336 1.015699 C -1.598882 -1.594905 1.745556 C -0.615522 -0.659404 2.401814 H -1.238628 -2.620928 1.656515 H 0.321185 -1.102714 2.730177 C -0.960243 0.525611 3.228002 H -1.753075 1.136980 2.788817 H -0.080328 1.166947 3.343165 H -1.269929 0.212433 4.229629 C -3.095920 -1.437416 1.626429 C -5.898265 -1.186856 1.271572 C -3.773755 -2.079880 0.569884 C -3.894684 -0.730295 2.540750 C -5.276428 -0.587005 2.359026 C -5.154341 -1.953920 0.384682 H -3.222423 -2.738878 -0.096919 H -3.462439 -0.298660 3.439758 H -5.863638 -0.030774 3.088033 H -5.648502 -2.478572 -0.430577 C -1.270735 -6.100831 -2.655225 C -1.323058 -7.027472 -1.420797 H -0.329495 -7.217975 -1.000851 H -1.753436 -8.002747 -1.676813 H -1.937987 -6.589724 -0.625439 C -0.357887 -6.731218 -3.729023 H 0.656780 -6.912097 -3.358043 H -0.275572 -6.080451 -4.607638 H -0.752281 -7.697327 -4.065154 C -2.699234 -6.049898 -3.243901 H -2.739264 -5.441049 -4.154637 H -3.417420 -5.638488 -2.524964 H -3.051654 -7.052988 -3.512872 C 2.682043 6.455689 1.724863 C 2.364353 7.325780 0.488959 H 2.920921 6.979598 -0.390054 H 2.634466 8.373901 0.663396 H 1.299780 7.309533 0.231445 C 1.842065 6.948062 2.923396 H 2.021853 6.329883 3.810979 H 0.766759 6.920542 2.716147 H 2.091557 7.983806 3.182030 C 4.166885 6.697914 2.079612 H 4.831417 6.399201 1.260492 H 4.462449 6.146484 2.979792 H 4.357532 7.759667 2.277429 Cl 0.690040 1.623377 -2.177688 Cl -7.583228 -0.983860 1.022218 Table 5, Entry i Co -0.131060 0.382749 -0.949704
125
N -1.297937 1.942667 -0.351072 N -1.797236 -0.063191 -2.018934 C -0.757370 2.946212 0.244872 H -1.436679 3.754561 0.561017 C -1.970516 -1.264591 -2.448515 H -2.900344 -1.466519 -3.005026 C 0.672513 3.149779 0.512737 C 3.288330 3.820651 1.154328 C 1.670418 2.174531 0.405570 C 0.993671 4.449464 0.936990 C 2.304656 4.815137 1.262594 C 3.013918 2.494884 0.739350 H 0.212242 5.204385 1.024657 H 4.308460 4.090803 1.413193 C -1.074760 -2.407800 -2.226277 C 0.420725 -4.722015 -1.929685 C -1.665122 -3.662981 -2.431760 C 0.272620 -2.307050 -1.859779 C 1.063386 -3.476249 -1.727526 C -0.935569 -4.847199 -2.274293 H -2.714518 -3.733972 -2.717030 H 1.000155 -5.635229 -1.822784 C -2.729640 1.766021 -0.743329 H -3.166082 1.081795 -0.011267 C -2.712549 1.109706 -2.139004 H -2.251514 1.776274 -2.880597 O 1.412778 0.873943 0.071431 O 0.887369 -1.095951 -1.682523 C -4.131945 0.769157 -2.581933 H -4.131649 0.334371 -3.588533 H -4.582802 0.027015 -1.910581 C -3.545422 3.054858 -0.774102 H -3.077745 3.795227 -1.435857 H -3.602360 3.504884 0.224031 C -4.970878 2.769097 -1.255969 H -5.524649 3.710717 -1.343342 H -5.490272 2.163981 -0.502214 C -4.998419 2.031562 -2.594446 H -6.031224 1.765729 -2.846626 H -4.641995 2.705533 -3.383463 C 4.167718 1.452753 0.693743 C 2.575398 -3.436682 -1.373179 C 3.920882 0.365291 1.761453 H 4.718696 -0.386498 1.751641 H 2.978192 -0.167037 1.619147 H 3.889114 0.803854 2.766223 C 4.283471 0.820465 -0.710252 H 5.140784 0.139163 -0.768416 H 4.418506 1.591828 -1.477642 H 3.408279 0.233471 -0.989786 C 2.770138 -2.805557 0.020058 H 2.220979 -3.365106 0.786711 H 2.421760 -1.773529 0.064074 H 3.828075 -2.795444 0.307346 C 3.359114 -2.641134 -2.440718 H 3.214934 -3.076868 -3.436606 H 4.434671 -2.648338 -2.227226
H 3.062495 -1.591826 -2.501336 C 3.254600 -4.830510 -1.305614 H 3.194482 -5.357255 -2.265266 H 2.804461 -5.464822 -0.532938 H 4.319576 -4.739343 -1.058458 C 5.572965 2.038372 0.998754 H 6.346998 1.263928 0.930021 H 5.632403 2.449933 2.013139 H 5.844416 2.827497 0.287668 N -0.738808 -0.739785 0.627526 C -1.353715 -1.717003 1.449260 C -0.399095 -0.714880 2.007238 H -1.014387 -2.740177 1.333548 H 0.590409 -1.077210 2.271871 C -2.790796 -1.595854 1.909925 C -0.991092 0.419173 2.779345 C -2.171265 2.608439 4.100579 C -2.383131 0.612666 2.769141 C -0.206817 1.333789 3.496684 C -0.791201 2.421077 4.150787 C -2.970901 1.704302 3.405525 H 0.872374 1.200136 3.560806 H -0.170935 3.110775 4.722216 H -4.050836 1.833799 3.394208 H -2.626116 3.441893 4.634060 Cl 0.515443 1.593732 -2.614492 C -1.618666 -6.215427 -2.488002 C -0.688717 -7.429519 -2.264363 H -0.292419 -7.451540 -1.242473 H 0.157947 -7.423598 -2.960689 H -1.225977 -8.372656 -2.421285 C -2.798943 -6.361335 -1.502114 H -2.459398 -6.264568 -0.463964 H -3.281758 -7.340146 -1.605603 H -3.573783 -5.604499 -1.665941 C -2.149119 -6.308697 -3.935023 H -1.338258 -6.176420 -4.661148 H -2.908778 -5.548949 -4.148732 H -2.610868 -7.284790 -4.124563 C 2.618903 6.252874 1.729262 C 1.827630 6.559370 3.019663 H 2.073333 5.842542 3.812230 H 0.744301 6.516551 2.862721 H 2.057086 7.563561 3.394915 C 2.208664 7.256615 0.629597 H 2.728705 7.043645 -0.311923 H 2.454062 8.284564 0.921214 H 1.133029 7.231757 0.424006 C 4.111750 6.505835 2.039873 H 4.741495 6.337174 1.158532 H 4.471769 5.858256 2.847831 H 4.278415 7.541208 2.360823 O -3.222638 -0.215234 2.061464 C -3.008481 -2.347281 3.231998 H -2.360584 -1.960599 4.026303 H -2.793458 -3.415990 3.124333 H -4.039729 -2.229891 3.583435
126
C -3.714648 -2.199066 0.843965 H -3.465743 -3.244880 0.634402 H -3.644819 -1.638683 -0.093315 H -4.763527 -2.144609 1.157203 Table 5, Entry j Co -0.035764 0.520316 -0.707983 N -1.181104 2.127619 -0.218020 N -1.687477 0.069903 -1.824404 C -0.614116 3.174555 0.271612 H -1.267003 4.036564 0.485166 C -1.831443 -1.116336 -2.301125 H -2.741337 -1.302941 -2.894453 C 0.818328 3.353504 0.553257 C 3.440329 3.973636 1.219380 C 1.770299 2.328036 0.601056 C 1.190204 4.679512 0.826551 C 2.507687 5.020655 1.154868 C 3.112027 2.620466 0.962858 H 0.446815 5.475759 0.787645 H 4.463015 4.225177 1.487056 C -0.929649 -2.258928 -2.110336 C 0.558116 -4.578085 -1.855223 C -1.487778 -3.500512 -2.460599 C 0.383904 -2.175574 -1.635281 C 1.169444 -3.350225 -1.511529 C -0.763640 -4.685902 -2.327370 H -2.508921 -3.541101 -2.834405 H 1.124770 -5.504096 -1.767958 C -2.610499 1.952377 -0.608124 H -3.050403 1.310166 0.153873 C -2.601983 1.241351 -1.974118 H -2.145059 1.879225 -2.743128 O 1.461055 1.014464 0.379782 O 0.987468 -0.984347 -1.340566 C -4.026481 0.886113 -2.391547 H -4.037870 0.419460 -3.383545 H -4.468176 0.165034 -1.692119 C -3.420176 3.242740 -0.685532 H -2.959509 3.950536 -1.386625 H -3.461721 3.736865 0.292396 C -4.852253 2.938570 -1.135170 H -5.406776 3.876137 -1.255051 H -5.362119 2.366077 -0.350079 C -4.896476 2.145500 -2.440734 H -5.932057 1.867645 -2.667337 H -4.553123 2.787368 -3.261721 C 4.207387 1.524869 1.097922 C 2.645624 -3.333847 -1.028132 C 3.818537 0.521933 2.207115 H 4.593028 -0.243428 2.335990 H 2.885530 -0.007586 2.002802 H 3.693012 1.033235 3.169151 C 4.404795 0.795771 -0.247314 H 5.202736 0.046879 -0.179160 H 4.677302 1.502126 -1.040462 H 3.510113 0.268357 -0.579009
C 2.736720 -2.737414 0.392227 H 2.111456 -3.300094 1.095669 H 2.415031 -1.696731 0.436520 H 3.766579 -2.762472 0.767620 C 3.516445 -2.525033 -2.014053 H 3.473473 -2.959608 -3.020034 H 4.566700 -2.518772 -1.699258 H 3.208388 -1.481156 -2.103967 C 3.303686 -4.736641 -0.935464 H 3.335599 -5.235763 -1.911091 H 2.772869 -5.387291 -0.230508 H 4.340194 -4.664011 -0.583409 C 5.609030 2.064093 1.491144 H 6.338389 1.248237 1.568758 H 5.592230 2.566931 2.465245 H 5.997026 2.766989 0.744533 N -0.681868 -0.556115 0.892880 C -1.318197 -1.736304 1.357093 C -0.751218 -0.721056 2.298903 H -0.764799 -2.665781 1.255075 H 0.175736 -0.957251 2.809326 C -1.753992 0.010238 3.164963 C -2.807347 -1.753995 1.220674 C -5.608843 -1.668103 0.932055 C -3.493237 -2.777452 0.552101 C -3.568620 -0.711623 1.778907 C -4.951858 -0.651809 1.620877 C -4.881923 -2.734244 0.405123 H -2.950573 -3.638610 0.165692 H -5.523674 0.160341 2.063993 H -5.404852 -3.550033 -0.092555 H -6.693811 -1.650578 0.838597 C -1.348026 -6.071067 -2.677744 C -1.316986 -6.978077 -1.428075 H -0.297244 -7.164256 -1.074119 H -1.765173 -7.956211 -1.638535 H -1.875472 -6.526292 -0.599547 C -0.511784 -6.719840 -3.801576 H 0.525706 -6.897263 -3.498225 H -0.489124 -6.082798 -4.693704 H -0.929454 -7.690093 -4.094914 C -2.813704 -6.025694 -3.167202 H -2.915738 -5.430221 -4.081930 H -3.480146 -5.602189 -2.406579 H -3.184978 -7.031873 -3.396289 C 2.883637 6.490843 1.441273 C 2.563891 7.357735 0.203645 H 3.101949 6.995702 -0.680493 H 2.854695 8.402142 0.366735 H 1.495694 7.358437 -0.038928 C 2.069135 7.006109 2.647739 H 2.250624 6.391145 3.537210 H 0.990716 6.995755 2.455626 H 2.340050 8.039158 2.895360 C 4.377290 6.709557 1.773608 H 5.024992 6.393026 0.947726 H 4.675704 6.159788 2.673864
127
H 4.589215 7.769239 1.960576 Cl 0.682920 1.658274 -2.395257 O -2.974250 0.337522 2.444693 C -1.158540 1.349468 3.616054 H -0.227270 1.211706 4.175924 H -1.866470 1.902467 4.243925 H -0.941891 1.990327 2.758672 C -2.097404 -0.808872 4.420972 H -1.210364 -0.979751 5.040733 H -2.510348 -1.790773 4.165521 H -2.855206 -0.297613 5.025305 Table 5, Entry k Co -0.130581 0.321712 -1.071583 N -1.312274 1.885678 -0.514797 N -1.786987 -0.154549 -2.146553 C -0.790827 2.890328 0.095093 H -1.481442 3.698498 0.386368 C -1.956968 -1.368527 -2.540771 H -2.884860 -1.588855 -3.093645 C 0.626204 3.093656 0.419883 C 3.210314 3.768689 1.175233 C 1.638719 2.134405 0.307959 C 0.915758 4.376965 0.912248 C 2.208296 4.741633 1.304210 C 2.969355 2.461761 0.685838 H 0.123144 5.119825 1.006142 H 4.218011 4.040728 1.477490 C -1.055142 -2.500829 -2.288801 C 0.459984 -4.797013 -1.955355 C -1.636952 -3.764171 -2.466510 C 0.293073 -2.382548 -1.929196 C 1.094172 -3.542711 -1.781087 C -0.897263 -4.939400 -2.289683 H -2.686348 -3.849021 -2.748065 H 1.047347 -5.703571 -1.835364 C -2.737783 1.703584 -0.930567 H -3.188251 1.040776 -0.185450 C -2.697863 1.015427 -2.310153 H -2.221921 1.664295 -3.058005 O 1.410472 0.839551 -0.066223 O 0.899254 -1.163980 -1.774010 C -4.108776 0.668595 -2.773641 H -4.089273 0.209576 -3.769267 H -4.576690 -0.055445 -2.094530 C -3.548143 2.994306 -1.008782 H -3.063651 3.717317 -1.677592 H -3.624643 3.468054 -0.023048 C -4.964867 2.702640 -1.512934 H -5.512594 3.644114 -1.633690 H -5.502029 2.117682 -0.755725 C -4.969291 1.933592 -2.833822 H -5.998046 1.665854 -3.100133 H -4.594336 2.587127 -3.631393 C 4.144850 1.444826 0.613650 C 2.609044 -3.485011 -1.440993 C 3.922205 0.333518 1.660760
H 4.726535 -0.410390 1.625213 H 2.981193 -0.201912 1.518199 H 3.899104 0.750257 2.674987 C 4.271619 0.839384 -0.802037 H 5.154645 0.193608 -0.879090 H 4.368663 1.627294 -1.558203 H 3.419641 0.219505 -1.082809 C 2.808951 -2.836217 -0.057086 H 2.272107 -3.392199 0.720761 H 2.449700 -1.807490 -0.023463 H 3.869069 -2.811598 0.221048 C 3.376974 -2.692961 -2.522802 H 3.221967 -3.134623 -3.514405 H 4.455127 -2.695489 -2.322579 H 3.077162 -1.644523 -2.584573 C 3.302017 -4.871491 -1.364530 H 3.236116 -5.409997 -2.317249 H 2.866619 -5.500781 -0.579411 H 4.368697 -4.767611 -1.130076 C 5.538604 2.055060 0.923671 H 6.330688 1.302676 0.823045 H 5.600262 2.434368 1.950365 H 5.781884 2.873641 0.236094 N -0.747212 -0.771427 0.528069 C -1.417018 -1.702190 1.360294 C -0.329419 -0.825311 1.886143 H -1.198451 -2.752609 1.205036 H 0.630346 -1.296175 2.080072 C -2.808053 -1.433343 1.894816 C -0.756499 0.337321 2.725072 C -1.624442 2.608482 4.157972 C -2.116132 0.691249 2.777757 C 0.153822 1.123427 3.445442 C -0.273099 2.251815 4.153255 C -2.550470 1.822230 3.467993 H 1.212329 0.865159 3.458304 H 0.457400 2.849101 4.700737 H -3.609037 2.078039 3.481922 Cl 0.521982 1.506862 -2.751740 C -1.569608 -6.317074 -2.476257 C -0.629869 -7.519179 -2.229802 H -0.231503 -7.517203 -1.208481 H 0.215405 -7.521085 -2.927833 H -1.160090 -8.469427 -2.366465 C -2.748260 -6.453851 -1.487164 H -2.409112 -6.334452 -0.451257 H -3.222943 -7.438461 -1.571608 H -3.529516 -5.706895 -1.665132 C -2.099927 -6.442207 -3.920909 H -1.290416 -6.317747 -4.649918 H -2.865381 -5.692418 -4.148693 H -2.554302 -7.425250 -4.091383 C 2.482569 6.155542 1.860731 C 1.636276 6.379059 3.133609 H 1.860722 5.621671 3.894174 H 0.560640 6.331860 2.931354 H 1.836128 7.363222 3.573283
128
C 2.101153 7.213462 0.802522 H 2.661036 7.059766 -0.127612 H 2.319553 8.226606 1.159965 H 1.034973 7.186417 0.552760 C 3.957925 6.409160 2.245195 H 4.624436 6.300197 1.381677 H 4.295535 5.720241 3.028261 H 4.096098 7.426211 2.631570 O -3.070628 -0.012599 2.080028 C -3.045131 -2.177569 3.217718 H -2.321114 -1.880050 3.984094 H -2.956827 -3.261653 3.087484 H -4.038940 -1.951699 3.620304 C -3.841718 -1.916818 0.869031 H -3.735489 -2.986675 0.659441 H -3.735113 -1.377368 -0.076853 H -4.862278 -1.727579 1.220677 C -2.054340 3.798865 4.829620 N -2.405735 4.794758 5.306154 Table 5, Entry l Co 0.036202 0.551032 -0.709681 N -1.100787 2.162234 -0.222393 N -1.611859 0.111584 -1.836802 C -0.528216 3.210747 0.257942 H -1.176462 4.078084 0.464372 C -1.754076 -1.069617 -2.326507 H -2.656908 -1.247325 -2.933312 C 0.905093 3.383014 0.540293 C 3.529556 3.990532 1.207920 C 1.850688 2.351727 0.596564 C 1.284676 4.708320 0.805754 C 2.603663 5.043040 1.134670 C 3.193422 2.637827 0.959287 H 0.546691 5.509255 0.759979 H 4.553335 4.237535 1.475846 C -0.862174 -2.218490 -2.129447 C 0.605592 -4.548053 -1.858638 C -1.426694 -3.455917 -2.483973 C 0.447561 -2.144344 -1.642650 C 1.223471 -3.324376 -1.511603 C -0.712850 -4.646551 -2.342234 H -2.443621 -3.489377 -2.869779 H 1.165098 -5.478094 -1.766933 C -2.531446 1.986571 -0.605829 H -2.964883 1.335006 0.154219 C -2.527060 1.284985 -1.977798 H -2.073732 1.927484 -2.744954 O 1.533615 1.038721 0.381681 O 1.056388 -0.956612 -1.344612 C -3.953715 0.928673 -2.388282 H -3.970447 0.469491 -3.383657 H -4.388306 0.200666 -1.691166 C -3.345684 3.274391 -0.667969 H -2.892621 3.988835 -1.367266 H -3.381597 3.761152 0.313897 C -4.779453 2.967836 -1.110236
H -5.338739 3.903934 -1.218869 H -5.281624 2.386646 -0.326524 C -4.828539 2.185247 -2.421977 H -5.864457 1.905329 -2.644509 H -4.492527 2.834988 -3.239794 C 4.282049 1.536541 1.102398 C 2.696835 -3.318120 -1.019206 C 3.884210 0.539884 2.214086 H 4.654870 -0.228236 2.349411 H 2.949994 0.013246 2.007885 H 3.756801 1.055691 3.173456 C 4.479160 0.801197 -0.239435 H 5.271835 0.047256 -0.165817 H 4.759023 1.502764 -1.034272 H 3.581938 0.278722 -0.572137 C 2.784324 -2.719940 0.400622 H 2.151836 -3.277480 1.101659 H 2.469274 -1.677093 0.441645 H 3.812012 -2.751156 0.781476 C 3.579243 -2.517343 -2.001374 H 3.539236 -2.953485 -3.006802 H 4.627613 -2.517875 -1.680306 H 3.278971 -1.471522 -2.095043 C 3.343901 -4.725584 -0.920395 H 3.378311 -5.226373 -1.895081 H 2.803802 -5.371245 -0.217907 H 4.378679 -4.660093 -0.561911 C 5.685483 2.069270 1.498002 H 6.409703 1.249477 1.581987 H 5.668177 2.576857 2.469628 H 6.080362 2.766248 0.749456 N -0.614683 -0.536668 0.893844 C -1.212182 -1.730431 1.375677 C -0.688673 -0.677544 2.302354 H -0.623113 -2.639883 1.292256 H 0.242675 -0.871109 2.823036 C -1.722741 0.031720 3.149789 C -2.700198 -1.810866 1.240207 C -5.509598 -1.842968 0.953025 C -3.344808 -2.879160 0.601381 C -3.503077 -0.786900 1.773265 C -4.888439 -0.782977 1.616062 C -4.736243 -2.895923 0.454353 H -2.766136 -3.724624 0.230457 H -5.480981 0.030942 2.031593 H -5.214863 -3.743746 -0.037711 C -1.303907 -6.027808 -2.697444 C -1.287256 -6.935835 -1.448182 H -0.271194 -7.129292 -1.087638 H -1.740698 -7.910756 -1.662269 H -1.848108 -6.480824 -0.623026 C -0.464374 -6.681154 -3.816059 H 0.569992 -6.865033 -3.505939 H -0.431904 -6.043827 -4.707678 H -0.886098 -7.648657 -4.112645 C -2.766086 -5.972493 -3.196255 H -2.858172 -5.377023 -4.112033
129
H -3.434311 -5.543741 -2.440131 H -3.142919 -6.976195 -3.427110 C 2.988582 6.512733 1.412108 C 2.677365 7.373305 0.167916 H 3.215111 7.001823 -0.712484 H 2.974580 8.416878 0.324656 H 1.609763 7.379297 -0.077189 C 2.174664 7.041412 2.613156 H 2.350048 6.431263 3.507156 H 1.096652 7.036836 2.418565 H 2.451771 8.074307 2.854489 C 4.482847 6.723969 1.746516 H 5.130398 6.397842 0.924258 H 4.775603 6.178220 2.651065 H 4.701200 7.783469 1.927010 Cl 0.761278 1.689121 -2.393896 O -2.950400 0.298253 2.415857 C -1.182172 1.400485 3.580141 H -0.247572 1.308999 4.143894 H -1.913133 1.934728 4.197812 H -0.989745 2.036053 2.713402 C -2.042332 -0.776781 4.419168 H -1.153439 -0.900844 5.047372 H -2.414513 -1.778918 4.180245 H -2.823709 -0.284525 5.009092 C -6.929768 -1.834948 0.761860 N -8.069202 -1.787936 0.557598 Table 5, Entry m Co -0.082321 0.698549 -0.505192 N -1.287264 2.245082 0.021476 N -1.693739 0.206567 -1.628690 C -0.772159 3.292577 0.563820 H -1.466119 4.111162 0.815691 C -1.785779 -0.975046 -2.126605 H -2.705835 -1.202088 -2.689657 C 0.649590 3.526145 0.853573 C 3.246757 4.233735 1.528315 C 1.643611 2.541574 0.863970 C 0.965784 4.856612 1.170767 C 2.269756 5.241715 1.505276 C 2.974178 2.877317 1.227775 H 0.189112 5.621202 1.161349 H 4.260132 4.519297 1.797248 C -0.793336 -2.053353 -2.034588 C 0.919858 -4.229391 -2.182964 C -1.259798 -3.300498 -2.481725 C 0.531267 -1.901743 -1.613586 C 1.440221 -2.987564 -1.743759 C -0.423792 -4.421003 -2.537747 H -2.297099 -3.415595 -2.796081 H 1.588449 -5.082365 -2.260771 C -2.712633 2.001347 -0.356998 H -3.111752 1.313374 0.396912 C -2.664870 1.335335 -1.746011 H -2.228528 2.020718 -2.486312 O 1.385014 1.224976 0.605591
O 1.034047 -0.740589 -1.100261 C -4.063436 0.938105 -2.205588 H -4.034827 0.515703 -3.217110 H -4.487095 0.168171 -1.550921 C -3.583462 3.253149 -0.400573 H -3.149446 4.006637 -1.070530 H -3.657448 3.710326 0.593280 C -4.994348 2.900225 -0.880024 H -5.590660 3.815220 -0.970425 H -5.486122 2.274550 -0.125151 C -4.986966 2.159500 -2.216754 H -6.006345 1.846618 -2.469672 H -4.661590 2.848549 -3.006238 C 4.118008 1.826343 1.305178 C 2.966562 -2.852044 -1.468666 C 3.771003 0.721352 2.328600 H 4.599360 0.011196 2.438235 H 2.895778 0.131594 2.048267 H 3.569872 1.152629 3.316456 C 4.360606 1.212692 -0.088936 H 5.177440 0.481853 -0.064339 H 4.627372 1.986802 -0.818300 H 3.483839 0.693900 -0.478293 C 3.230398 -2.488426 0.004705 H 2.809382 -3.247019 0.674483 H 2.802992 -1.525636 0.287021 H 4.305385 -2.424701 0.211365 C 3.572939 -1.781213 -2.404318 H 3.412159 -2.045661 -3.456455 H 4.653921 -1.685896 -2.247261 H 3.145159 -0.787326 -2.255581 C 3.782762 -4.146408 -1.733166 H 3.694234 -4.476731 -2.774845 H 3.463852 -4.967397 -1.080255 H 4.850936 -3.985977 -1.540973 C 5.486492 2.401411 1.758940 H 6.250760 1.615473 1.801231 H 5.427818 2.843071 2.760692 H 5.857355 3.164383 1.064456 N -0.828885 -0.284794 1.101073 C -0.445851 -0.821535 2.347011 C -1.880375 -0.808009 1.895601 H -0.130554 -0.102867 3.096308 H -2.535779 -0.112020 2.405710 C 0.281322 -2.116772 2.488460 H 0.404018 -2.308758 3.562144 H 1.290837 -2.021306 2.081502 Cl 0.644448 1.836015 -2.188335 C -0.978604 -5.785250 -2.999752 C 0.058156 -6.931334 -2.975467 H 0.460603 -7.089765 -1.968110 H 0.896946 -6.732273 -3.652611 H -0.392728 -7.878558 -3.295223 C -2.141193 -6.208728 -2.074529 H -1.812970 -6.264267 -1.029683 H -2.530775 -7.194360 -2.354998 H -2.983223 -5.509380 -2.117537
130
C -1.497153 -5.668851 -4.449117 H -0.700918 -5.339557 -5.127218 H -2.321687 -4.953216 -4.538705 H -1.868998 -6.633280 -4.814455 C 2.585237 6.715880 1.840183 C 1.754634 7.156184 3.065230 H 1.964846 6.519879 3.933099 H 0.676853 7.107534 2.875472 H 1.983421 8.190735 3.346779 C 2.224873 7.609491 0.633120 H 2.774369 7.300196 -0.263911 H 2.472217 8.659154 0.830542 H 1.156692 7.573307 0.393158 C 4.069707 6.985545 2.176214 H 4.726876 6.725547 1.338170 H 4.394459 6.417761 3.055940 H 4.237734 8.046069 2.399490 C -2.550705 -2.078591 1.429370 H -2.373965 -2.176425 0.353492 C -1.930230 -3.292560 2.130270 H -2.380709 -4.214386 1.744052 H -2.121269 -3.262270 3.209987 C -0.424139 -3.321972 1.875365 H -0.241858 -3.348868 0.797353 H 0.006504 -4.242396 2.286017 C -4.071913 -2.023111 1.615073 O -4.447744 -1.845395 2.976191 C -5.763831 -1.304560 2.871563 C -5.634126 -0.364826 1.696626 O -4.625597 -0.937655 0.840370 H -4.522313 -2.953391 1.244334 H -6.465512 -2.120331 2.664893 H -6.056121 -0.801972 3.796820 H -5.263540 0.614612 2.016305 H -6.568880 -0.227383 1.147015 Table 5, Entry n Co 0.039014 0.627548 -0.687988 N -1.220779 2.063672 0.017906 N -1.579296 0.203818 -1.838706 C -0.739063 3.044461 0.697810 H -1.461495 3.797457 1.053273 C -1.704510 -0.969534 -2.351679 H -2.624247 -1.167262 -2.926296 C 0.676613 3.297491 1.006219 C 3.253096 4.060576 1.705945 C 1.727017 2.387791 0.835085 C 0.927637 4.579824 1.521934 C 2.217473 4.991615 1.877438 C 3.051004 2.754677 1.197441 H 0.108836 5.287175 1.654005 H 4.257167 4.365999 1.987465 C -0.752222 -2.079852 -2.219797 C 0.865651 -4.326763 -2.124237 C -1.277290 -3.342264 -2.528690 C 0.591593 -1.937888 -1.850273 C 1.444839 -3.069442 -1.823818
C -0.486103 -4.495164 -2.469522 H -2.323818 -3.443205 -2.814989 H 1.492809 -5.213873 -2.095145 C -2.629857 1.877007 -0.463652 H -3.073403 1.118310 0.186914 C -2.508620 1.364982 -1.913142 H -2.001029 2.111510 -2.539774 O 1.542163 1.106450 0.395529 O 1.140495 -0.715440 -1.561609 C -3.867435 1.077921 -2.535542 H -3.755503 0.782398 -3.585861 H -4.367890 0.249683 -2.028738 C -3.484687 3.140701 -0.421476 H -2.994711 3.960655 -0.962482 H -3.627447 3.477456 0.612183 C -4.859860 2.876497 -1.041773 H -5.441116 3.805466 -1.052837 H -5.409151 2.164468 -0.413114 C -4.758919 2.319618 -2.461721 H -5.760403 2.075247 -2.833561 H -4.354156 3.094752 -3.124370 C 4.260691 1.784062 1.075314 C 2.956733 -2.978353 -1.478467 C 4.069679 0.592914 2.038626 H 4.913193 -0.104630 1.976728 H 3.165309 0.017343 1.832372 H 3.998239 0.937443 3.077356 C 4.419377 1.287367 -0.378245 H 5.309633 0.656240 -0.486084 H 4.523042 2.130552 -1.071406 H 3.575810 0.687452 -0.721025 C 3.134432 -2.471060 -0.033566 H 2.625310 -3.128921 0.680833 H 2.732175 -1.467870 0.109162 H 4.193708 -2.430343 0.245988 C 3.682569 -2.042382 -2.470727 H 3.544837 -2.384996 -3.503220 H 4.760380 -2.014929 -2.270551 H 3.333350 -1.008607 -2.423305 C 3.712246 -4.332102 -1.549594 H 3.664253 -4.770122 -2.553508 H 3.311119 -5.059538 -0.834109 H 4.774685 -4.204798 -1.307555 C 5.629394 2.415695 1.447537 H 6.444655 1.691721 1.325721 H 5.655994 2.744196 2.493150 H 5.865519 3.274269 0.807888 N -0.439635 -0.713231 0.787589 C -0.962986 -1.871214 1.396958 C -0.021265 -0.946349 2.121966 H -0.553967 -2.819797 1.058522 H 1.003880 -1.268234 2.266573 C -2.362605 -2.022913 1.917583 H -2.310692 -2.862976 2.626758 Cl 0.630615 2.032363 -2.216654 C -1.100821 -5.875779 -2.785312 C -0.109439 -7.054531 -2.657796
131
H 0.295549 -7.133126 -1.642116 H 0.730340 -6.953440 -3.355138 H -0.599902 -8.009173 -2.883350 C -2.265533 -6.155881 -1.809597 H -1.924189 -6.120482 -0.768122 H -2.698741 -7.147474 -1.985501 H -3.079049 -5.429516 -1.913053 C -1.636138 -5.884872 -4.233415 H -0.838030 -5.657044 -4.949906 H -2.434104 -5.150004 -4.385795 H -2.050058 -6.865590 -4.495608 C 2.456427 6.410950 2.437012 C 1.643661 6.597389 3.736777 H 1.920316 5.845787 4.485664 H 0.564720 6.511496 3.568020 H 1.820875 7.586400 4.175373 C 2.002781 7.459835 1.398129 H 2.538941 7.332793 0.450149 H 2.193777 8.478516 1.755548 H 0.931129 7.393618 1.181129 C 3.932908 6.718009 2.776200 H 4.575187 6.639283 1.891290 H 4.320975 6.037992 3.543501 H 4.045067 7.737381 3.164912 C -0.500998 -0.011098 3.187286 H -0.614504 0.997156 2.777680 C -1.819005 -0.455845 3.809312 H -2.211254 0.345261 4.445886 H -1.647758 -1.324422 4.457292 C -2.843074 -0.816030 2.735205 H -3.014207 0.053975 2.095696 H -3.797668 -1.051536 3.219046 H 0.258136 0.062957 3.974723 C -3.344691 -2.457926 0.818667 O -4.469822 -3.115696 1.407940 C -5.609908 -2.341403 1.056336 C -5.185128 -1.654632 -0.210876 O -3.794800 -1.348898 0.006640 H -2.867636 -3.183969 0.150433 H -6.490436 -2.976471 0.932473 H -5.795162 -1.620879 1.859418 H -5.248679 -2.323064 -1.076467 H -5.752129 -0.742809 -0.412647 Table 5, Entry o Co -0.151173 0.364278 -0.758221 N -1.513296 1.751462 -0.164149 N -1.745142 -0.272977 -1.875592 C -1.100273 2.849575 0.364678 H -1.872074 3.584689 0.645564 C -1.734620 -1.457478 -2.378524 H -2.619014 -1.754674 -2.965438 C 0.297418 3.237932 0.608690 C 2.813843 4.230140 1.229101 C 1.398551 2.372140 0.579587 C 0.468393 4.591664 0.937914 C 1.727688 5.119325 1.246459
C 2.691137 2.855266 0.913705 H -0.391300 5.261370 0.961191 H 3.794098 4.626935 1.479178 C -0.693555 -2.477064 -2.190217 C 1.080363 -4.584723 -1.934414 C -1.105204 -3.786715 -2.488444 C 0.611598 -2.220799 -1.751359 C 1.543594 -3.282759 -1.634975 C -0.233082 -4.868367 -2.356229 H -2.125709 -3.962216 -2.823143 H 1.761498 -5.430464 -1.850413 C -2.911631 1.361688 -0.518483 H -3.211255 0.609845 0.218314 C -2.829759 0.752570 -1.934452 H -2.487091 1.503594 -2.659756 O 1.285725 1.033666 0.317146 O 1.059044 -0.955844 -1.481902 C -4.191883 0.222515 -2.372086 H -4.147100 -0.163647 -3.397347 H -4.515694 -0.606832 -1.731796 C -3.917125 2.509031 -0.491175 H -3.589631 3.330012 -1.142096 H -4.011704 2.918630 0.521619 C -5.293051 2.018386 -0.949249 H -5.990492 2.862862 -0.985917 H -5.688478 1.310921 -0.209602 C -5.239880 1.337634 -2.316615 H -6.225993 0.927127 -2.561649 H -5.008670 2.087913 -3.083073 C 3.947315 1.940143 0.962591 C 3.019981 -3.070049 -1.202716 C 3.767345 0.859108 2.051487 H 4.651341 0.213798 2.116627 H 2.911870 0.204389 1.871871 H 3.617321 1.318100 3.036170 C 4.193760 1.288049 -0.414136 H 5.104403 0.677353 -0.406205 H 4.310165 2.049960 -1.194006 H 3.381979 0.629814 -0.724591 C 3.075335 -2.469737 0.217288 H 2.560692 -3.116255 0.938108 H 2.609658 -1.485881 0.277981 H 4.110747 -2.349110 0.557026 C 3.743736 -2.149018 -2.209364 H 3.715465 -2.575703 -3.219191 H 4.796709 -2.014665 -1.934613 H 3.306725 -1.150109 -2.271064 C 3.862244 -4.372364 -1.142224 H 3.918887 -4.864627 -2.120224 H 3.453315 -5.086628 -0.417892 H 4.893421 -4.161664 -0.832649 C 5.265942 2.679439 1.315638 H 6.116205 1.986247 1.327505 H 5.220591 3.139723 2.309651 H 5.501374 3.459828 0.582422 N -0.630250 -0.836369 0.825127 C -1.110049 -2.078071 1.321886
132
C -0.703422 -0.960375 2.240231 H -0.415268 -2.910476 1.251855 H 0.247698 -1.138192 2.744403 C -2.511058 -2.455706 1.035458 C -1.560035 0.107247 2.880629 C -3.037874 2.227864 4.056059 C -2.947465 0.016726 3.075317 C -0.936701 1.283387 3.350003 C -1.659897 2.333188 3.922359 C -3.680456 1.066211 3.642415 H -3.493945 -0.886831 2.822940 H 0.148731 1.373908 3.299515 H -1.142774 3.213088 4.301889 H -4.752598 0.957856 3.802019 H -3.605083 3.025417 4.533442 Cl 0.361050 1.657982 -2.408323 C -0.648708 -6.323910 -2.659894 C -0.462013 -7.191335 -1.395779 H -1.045875 -6.795126 -0.556404 H 0.584141 -7.239337 -1.074708 H -0.789121 -8.222700 -1.572443 C -2.123308 -6.474756 -3.098645 H -2.813103 -6.121413 -2.323230 H -2.371313 -7.524659 -3.295961 H -2.329463 -5.917875 -4.020122 C 0.225844 -6.887715 -3.800454 H 1.286769 -6.926527 -3.530627 H 0.138746 -6.273213 -4.704353 H -0.075198 -7.909151 -4.061109 C 1.879659 6.614689 1.600361 C 1.038928 6.934918 2.855526 H 1.346425 6.313332 3.704876 H -0.030895 6.763680 2.693647 H 1.153853 7.984357 3.151071 C 1.383538 7.479559 0.420889 H 1.938870 7.250504 -0.496392 H 1.513507 8.547547 0.631733 H 0.320190 7.323581 0.209129 C 3.331843 7.049889 1.901810 H 3.990625 6.880169 1.042166 H 3.744904 6.510856 2.762381 H 3.382332 8.119338 2.139546 O -3.157710 -1.905048 0.149455 O -2.930778 -3.454867 1.843906 C -4.268899 -3.902127 1.608883 H -4.977452 -3.084942 1.775408 H -4.488163 -4.705275 2.317465 H -4.364374 -4.296049 0.592321 Table 5, Entry p Co -0.056457 0.489315 -0.585350 N -1.170770 2.116254 -0.107893 N -1.712277 0.051238 -1.689318 C -0.592469 3.162051 0.370190 H -1.239252 4.025315 0.596621 C -1.841787 -1.116132 -2.212809 H -2.745888 -1.284231 -2.820358
C 0.844405 3.331900 0.627429 C 3.482090 3.934840 1.242789 C 1.785155 2.296416 0.680812 C 1.234141 4.658362 0.870803 C 2.560044 4.990972 1.172437 C 3.135248 2.580453 1.017665 H 0.497212 5.460444 0.829640 H 4.511272 4.180311 1.490265 C -0.936069 -2.261125 -2.057117 C 0.533635 -4.598220 -1.851409 C -1.473842 -3.481134 -2.506049 C 0.352802 -2.207289 -1.515559 C 1.125903 -3.393027 -1.408020 C -0.758813 -4.674733 -2.402107 H -2.475514 -3.499251 -2.931003 H 1.093769 -5.529784 -1.784456 C -2.612753 1.922576 -0.433009 H -3.011968 1.265102 0.345125 C -2.642116 1.217648 -1.803214 H -2.214010 1.863217 -2.582571 O 1.455124 0.982165 0.491563 O 0.957016 -1.037686 -1.147398 C -4.075500 0.851797 -2.178550 H -4.114777 0.397512 -3.175470 H -4.485425 0.116799 -1.475460 C -3.440846 3.201962 -0.472353 H -3.015673 3.920232 -1.185143 H -3.451983 3.689481 0.509723 C -4.883520 2.880683 -0.872294 H -5.455734 3.810904 -0.962552 H -5.356149 2.292666 -0.075474 C -4.962224 2.100450 -2.183919 H -6.001390 1.811594 -2.378096 H -4.655297 2.755124 -3.009218 C 4.221074 1.476409 1.157960 C 2.576468 -3.410936 -0.850895 C 3.837728 0.496789 2.289546 H 4.607887 -0.272094 2.423449 H 2.898902 -0.029527 2.104732 H 3.726968 1.026219 3.243520 C 4.390797 0.721474 -0.176184 H 5.182074 -0.034293 -0.106686 H 4.657552 1.410219 -0.986560 H 3.485153 0.197815 -0.482697 C 2.621243 -2.819292 0.574574 H 1.932181 -3.350142 1.242124 H 2.355139 -1.762666 0.606451 H 3.627143 -2.896094 1.004315 C 3.504818 -2.620246 -1.797118 H 3.517767 -3.069773 -2.797428 H 4.535338 -2.611560 -1.423185 H 3.201049 -1.578621 -1.922218 C 3.197221 -4.828664 -0.729440 H 3.283616 -5.321133 -1.705095 H 2.606597 -5.472631 -0.067203 H 4.210537 -4.781624 -0.311647 C 5.633651 2.007499 1.521689
133
H 6.355380 1.185374 1.604329 H 5.635714 2.528343 2.486425 H 6.018670 2.692206 0.756860 N -0.748007 -0.540626 1.043803 C -1.397903 -1.595435 1.741703 C -0.717954 -0.469967 2.465430 H -0.839761 -2.532054 1.793851 H 0.242087 -0.707589 2.916029 C -1.435191 0.611039 3.174534 C -2.856791 -1.760000 1.370912 C -5.542010 -2.204973 0.541810 C -3.220978 -2.851065 0.553546 C -3.908868 -0.931111 1.794163 C -5.230645 -1.141505 1.380210 C -4.536242 -3.069925 0.134438 H -2.465016 -3.581776 0.264961 H -3.742953 -0.113195 2.486646 H -6.027058 -0.495560 1.747420 H -4.781297 -3.940377 -0.471768 H -6.574675 -2.388440 0.249770 C -1.324629 -6.035839 -2.860093 C -1.369427 -7.008077 -1.660973 H -0.372764 -7.217527 -1.257675 H -1.805954 -7.971464 -1.949466 H -1.975391 -6.598233 -0.844067 C -0.425032 -6.628543 -3.965912 H 0.592154 -6.828295 -3.611949 H -0.347805 -5.944804 -4.819589 H -0.827284 -7.579202 -4.335150 C -2.758578 -5.956621 -3.432236 H -2.805333 -5.310327 -4.316458 H -3.468678 -5.573559 -2.689927 H -3.116753 -6.946760 -3.738921 C 2.955725 6.461939 1.425596 C 2.624447 7.309636 0.177726 H 3.143928 6.925911 -0.708372 H 2.928753 8.353662 0.316870 H 1.552423 7.317376 -0.047206 C 2.166705 7.007628 2.635596 H 2.356703 6.407138 3.533142 H 1.085191 7.005024 2.461442 H 2.452191 8.042129 2.859656 C 4.456884 6.670743 1.729223 H 5.087433 6.331859 0.898947 H 4.764450 6.134719 2.634672 H 4.682940 7.731387 1.892711 Cl 0.685552 1.574130 -2.297166 O -1.635949 0.297372 4.474797 C -2.307808 1.300330 5.242123 H -1.725811 2.227046 5.249767 H -2.400555 0.937016 6.269090 H -3.310691 1.476381 4.841123 O -1.779750 1.642160 2.606709 Table 6, Entry a Mn 0.550458 -0.055887 -0.393030 N 2.099367 1.177714 -0.305935
N 1.920482 -1.433588 -0.001745 C 2.013335 2.453397 -0.158999 H 2.935262 3.035258 -0.117687 C 1.674867 -2.698244 -0.000003 H 2.507589 -3.388561 0.143147 C 0.799671 3.211520 -0.037158 C -1.426534 4.851106 0.158126 C -0.506153 2.625747 -0.121058 C 0.954000 4.600920 0.156394 C -0.147291 5.420452 0.258992 C -1.653354 3.489759 -0.028273 H 1.959104 5.011449 0.223172 H -2.278838 5.515142 0.234086 C 0.382974 -3.311513 -0.123851 C -2.033714 -4.670230 -0.120255 C 0.361122 -4.722436 -0.178147 C -0.840159 -2.562669 -0.085061 C -2.087824 -3.282450 -0.037263 C -0.835158 -5.400995 -0.200519 H 1.305956 -5.261010 -0.200278 H -2.959821 -5.232339 -0.110009 C 3.364538 0.451669 -0.494878 H 3.400865 0.187791 -1.562443 C 3.247503 -0.863805 0.304669 H 3.204095 -0.593007 1.366785 O -0.704086 1.335423 -0.297293 O -0.870489 -1.248723 -0.086022 C 4.458191 -1.770656 0.054870 H 4.396070 -2.675462 0.669382 H 4.471100 -2.090578 -0.996694 C 4.650321 1.201593 -0.130773 H 4.607478 1.510354 0.922754 H 4.746446 2.111743 -0.734590 C 5.874139 0.301457 -0.367097 H 6.784602 0.834457 -0.069627 H 5.969059 0.095763 -1.442584 C 5.759239 -1.023107 0.397301 H 6.620154 -1.665127 0.177035 H 5.784184 -0.823891 1.477565 C -3.086267 2.936929 -0.148769 C -3.431485 -2.547965 0.123351 C -3.276711 2.291333 -1.543349 H -4.289165 1.879118 -1.631184 H -2.561489 1.485037 -1.711152 H -3.147043 3.038448 -2.336050 C -3.345350 1.901702 0.970256 H -4.365848 1.508109 0.883960 H -3.246307 2.367980 1.957784 H -2.645194 1.069749 0.914931 C -3.653147 -1.553026 -1.041294 H -3.656138 -2.079848 -2.003871 H -2.880803 -0.785565 -1.069065 H -4.626096 -1.059575 -0.926382 C -3.438991 -1.807333 1.483990 H -3.383736 -2.526119 2.310433 H -4.369908 -1.237495 1.594576 H -2.600101 -1.116235 1.577367
134
C -4.630192 -3.518491 0.120671 H -4.586539 -4.241921 0.943456 H -4.715050 -4.070613 -0.823287 H -5.553189 -2.941271 0.243940 C -4.152447 4.043004 -0.005394 H -5.146111 3.589242 -0.089545 H -4.075557 4.805224 -0.790324 H -4.102424 4.542461 0.969397 Cl 0.714208 0.185888 2.064577 H -0.861600 -6.484814 -0.255966 H -0.036254 6.489483 0.411309 O 0.747394 -0.219350 -1.930125 Table 6, Entry b Mn 0.471107 -0.051730 -0.132229 N 2.052595 1.158436 -0.366784 N 1.894542 -1.421741 0.148073 C 1.992469 2.449215 -0.332865 H 2.925172 3.008290 -0.418564 C 1.685458 -2.697283 0.072873 H 2.548609 -3.359889 0.148630 C 0.810934 3.246877 -0.186489 C -1.388416 4.908801 0.068505 C -0.502719 2.683275 -0.223620 C 0.990825 4.640189 -0.033100 C -0.098917 5.468714 0.100651 C -1.638214 3.548670 -0.094544 H 2.001794 5.041272 -0.014472 H -2.229798 5.582615 0.178370 C 0.422881 -3.353231 -0.086595 C -1.954194 -4.762596 -0.279976 C 0.443460 -4.756451 -0.264809 C -0.821233 -2.647349 -0.008031 C -2.049650 -3.386996 -0.093707 C -0.733538 -5.457829 -0.372610 H 1.402825 -5.266463 -0.318475 H -2.865272 -5.344688 -0.355401 C 3.301547 0.402942 -0.567372 H 3.267332 0.021945 -1.597639 C 3.217455 -0.817196 0.377891 H 3.191889 -0.432987 1.406311 O -0.689800 1.394028 -0.428525 O -0.855812 -1.350846 0.195998 C 4.426513 -1.742924 0.207539 H 4.379308 -2.569551 0.926060 H 4.416653 -2.183119 -0.799690 C 4.606236 1.180618 -0.360108 H 4.608758 1.626821 0.643958 H 4.675745 2.002184 -1.082804 C 5.820390 0.249992 -0.520271 H 6.740150 0.815434 -0.329896 H 5.876659 -0.097313 -1.561545 C 5.732336 -0.959812 0.417855 H 6.588447 -1.625730 0.259308 H 5.787766 -0.619588 1.461184 C -3.074699 2.993270 -0.135556 C -3.414000 -2.683706 0.033933
C -3.345429 2.348082 -1.516506 H -4.367592 1.951374 -1.548319 H -2.653784 1.529503 -1.722934 H -3.248121 3.091833 -2.316937 C -3.274132 1.954457 0.994008 H -4.296169 1.557025 0.955645 H -3.129097 2.419112 1.976305 H -2.576947 1.120805 0.909299 C -3.573176 -1.620928 -1.079608 H -3.518746 -2.087284 -2.070806 H -2.803682 -0.850522 -1.019686 H -4.552725 -1.135075 -0.990052 C -3.528111 -2.021571 1.428912 H -3.469567 -2.777466 2.221316 H -4.493940 -1.509820 1.521823 H -2.734779 -1.291177 1.592555 C -4.588562 -3.673211 -0.107731 H -4.581201 -4.446372 0.670035 H -4.598403 -4.167796 -1.086412 H -5.530813 -3.122885 -0.010981 C -4.128574 4.100491 0.071356 H -5.126591 3.649028 0.051432 H -4.099847 4.861454 -0.718142 H -4.016376 4.602764 1.039576 Cl 0.586684 0.435912 2.157979 H -0.731615 -6.533503 -0.518715 H 0.025353 6.539322 0.230779 O 0.553186 -0.449402 -1.842111 Table 6, Entry c Mn -0.333238 -0.366455 0.082145 N -2.287343 -0.553086 0.330155 N -0.409753 -2.343152 -0.149778 C -3.138938 0.424155 0.292859 H -4.195947 0.186159 0.412849 C 0.609657 -3.138990 -0.164608 H 0.422683 -4.208722 -0.261687 C -2.841799 1.811409 0.115131 C -2.390976 4.540475 -0.129689 C -1.495956 2.311537 0.118816 C -3.933717 2.701343 -0.000938 C -3.713766 4.052344 -0.130631 C -1.271255 3.729241 -0.001518 H -4.944722 2.300480 0.006742 H -2.254746 5.610425 -0.234927 C 1.992244 -2.769072 -0.076257 C 4.699389 -2.177763 0.082623 C 2.943363 -3.811264 -0.064395 C 2.415119 -1.402023 -0.004988 C 3.819302 -1.100974 0.076632 C 4.287425 -3.521816 0.015977 H 2.598096 -4.841386 -0.117431 H 5.763572 -1.983257 0.143254 C -2.676136 -1.952297 0.593580 H -2.368652 -2.162025 1.626266 C -1.795964 -2.816706 -0.335962 H -2.053405 -2.546044 -1.369125
135
O -0.479129 1.508403 0.270360 O 1.545072 -0.425959 -0.019213 C -2.047094 -4.313691 -0.121310 H -1.468550 -4.904212 -0.840903 H -1.711738 -4.604238 0.884692 C -4.163197 -2.282523 0.430302 H -4.496531 -1.993464 -0.576548 H -4.761436 -1.709809 1.148685 C -4.410134 -3.784635 0.644587 H -5.471412 -4.006637 0.482505 H -4.192477 -4.046187 1.689696 C -3.540549 -4.636642 -0.286936 H -3.707169 -5.702833 -0.094331 H -3.837086 -4.456486 -1.329690 C 0.154756 4.309292 -0.003155 C 4.323230 0.353313 0.136728 C 0.856826 3.985368 1.338477 H 1.876407 4.389952 1.330119 H 0.916787 2.910770 1.513568 H 0.320075 4.443841 2.178104 C 0.959200 3.717179 -1.186236 H 1.970058 4.143297 -1.196931 H 0.480275 3.961097 -2.141637 H 1.041204 2.632089 -1.116878 C 3.728536 1.075787 1.370921 H 4.011359 0.559270 2.296195 H 2.640418 1.126258 1.325606 H 4.120932 2.099098 1.424549 C 3.922897 1.094288 -1.162324 H 4.400457 0.632421 -2.034975 H 4.253213 2.138986 -1.110145 H 2.843518 1.083760 -1.318086 C 5.859264 0.425085 0.257539 H 6.366100 -0.030451 -0.601307 H 6.226482 -0.055232 1.172356 H 6.163803 1.476726 0.293774 C 0.152881 5.843154 -0.164923 H 1.187984 6.201475 -0.157949 H -0.373624 6.347035 0.654380 H -0.297637 6.159447 -1.113125 Cl -0.628004 -0.183181 -2.247944 H 5.027754 -4.315853 0.027259 H -4.544485 4.743892 -0.232547 O -0.215971 -0.570991 1.839083 Table 7, Entry a C 0.669225 0.000000 -0.668187 H 1.169774 0.000000 -1.637322 C -0.669225 0.000000 -0.668187 H -1.169774 0.000000 -1.637322 C -1.592476 0.000000 0.518279 H -1.059056 0.000000 1.472957 H -2.249660 -0.880177 0.502462 H -2.249660 0.880177 0.502462 C 1.592476 0.000000 0.518279 H 2.249660 0.880177 0.502462 H 2.249660 -0.880177 0.502462
H 1.059056 0.000000 1.472957 Table 7, Entry b O 0.535717 -1.135211 0.000000 C -0.427735 -0.363645 -0.737910 C -0.427735 -0.363645 0.737910 H -1.191811 -0.979721 -1.220917 H -1.191811 -0.979721 1.220917 C 0.095728 0.754599 -1.604997 H 0.855590 1.348749 -1.091162 H -0.722445 1.418558 -1.909734 H 0.550390 0.343654 -2.514030 C 0.095728 0.754599 1.604997 H 0.550390 0.343654 2.514030 H -0.722445 1.418558 1.909734 H 0.855590 1.348749 1.091162 Table 8, Entry a Mn 0.542007 -0.061267 0.332604 N 2.147877 1.138336 -0.004980 N 1.844368 -1.404100 -0.089041 C 2.124252 2.427037 -0.014558 H 3.056047 2.980325 -0.152691 C 1.553269 -2.647426 -0.386656 H 2.383639 -3.327772 -0.576146 C 0.932787 3.231643 0.061167 C -1.280977 4.884443 -0.084555 C -0.353983 2.655110 -0.140191 C 1.085589 4.625914 0.189821 C -0.017318 5.451607 0.137425 C -1.492923 3.514841 -0.248658 H 2.083482 5.035796 0.330262 H -2.131274 5.554267 -0.136318 C 0.262961 -3.239955 -0.456674 C -2.169665 -4.578437 -0.475860 C 0.201045 -4.602648 -0.852917 C -0.932858 -2.537575 -0.070334 C -2.187801 -3.252816 -0.070494 C -0.999112 -5.263076 -0.872882 H 1.121864 -5.109067 -1.134023 H -3.098398 -5.137312 -0.487338 C 3.380191 0.417392 -0.376932 H 3.364705 0.326335 -1.475572 C 3.236780 -0.996270 0.191927 H 3.292682 -0.915214 1.287208 O -0.504996 1.337595 -0.263782 O -0.891650 -1.283874 0.292148 C 4.370542 -1.906295 -0.290628 H 4.282866 -2.903847 0.155477 H 4.313298 -2.031900 -1.381739 C 4.719154 1.041644 0.038564 H 4.733408 1.168376 1.129491 H 4.845735 2.036135 -0.403621 C 5.882422 0.141188 -0.412242 H 6.832126 0.565361 -0.065372 H 5.927794 0.134571 -1.510896 C 5.729248 -1.296846 0.099619
136
H 6.539621 -1.925764 -0.287420 H 5.822235 -1.305624 1.194587 C -2.906362 2.954357 -0.497223 C -3.497635 -2.563858 0.355628 C -2.932491 2.152549 -1.821263 H -3.939467 1.755665 -1.999783 H -2.232137 1.317524 -1.797617 H -2.672321 2.799480 -2.668395 C -3.318896 2.057975 0.694312 H -4.319345 1.641800 0.524426 H -3.350029 2.644113 1.620467 H -2.620656 1.232072 0.834617 C -3.809516 -1.406846 -0.621811 H -3.959443 -1.790979 -1.638439 H -3.003768 -0.673391 -0.645304 H -4.731058 -0.896738 -0.315794 C -3.377547 -2.031218 1.804519 H -3.194889 -2.855127 2.505162 H -4.314842 -1.543225 2.099240 H -2.566241 -1.310063 1.907495 C -4.700374 -3.528146 0.320213 H -4.572891 -4.378992 1.000096 H -4.892339 -3.917294 -0.686851 H -5.599082 -2.987351 0.636522 C -3.962184 4.071682 -0.625021 H -4.939020 3.617395 -0.824384 H -3.743191 4.755989 -1.453199 H -4.059823 4.661154 0.294180 Cl 0.904157 0.193648 2.521266 H -1.059489 -6.304213 -1.175154 H 0.084424 6.526628 0.251579 Table 8, Entry b Mn 0.506258 -0.059989 0.158535 N 2.063089 1.047349 -0.355978 N 1.861245 -1.499236 0.109975 C 2.039067 2.343240 -0.475803 H 2.973321 2.857218 -0.704021 C 1.626803 -2.775734 0.078393 H 2.472975 -3.460705 0.145435 C 0.898027 3.194940 -0.338901 C -1.235956 4.946916 -0.091358 C -0.425198 2.673603 -0.174009 C 1.117500 4.591456 -0.400300 C 0.061172 5.462564 -0.280547 C -1.524727 3.587628 -0.033624 H 2.132153 4.960151 -0.535542 H -2.044980 5.659933 0.018480 C 0.344193 -3.403902 -0.037040 C -2.075385 -4.734198 -0.274743 C 0.313291 -4.816819 -0.062967 C -0.866620 -2.648086 -0.131040 C -2.116527 -3.342989 -0.259101 C -0.885832 -5.480293 -0.179851 H 1.249427 -5.366179 0.012107 H -3.003773 -5.286456 -0.362714 C 3.311292 0.282862 -0.590331
H 3.279294 -0.066123 -1.635009 C 3.219200 -0.960824 0.310265 H 3.242975 -0.611579 1.352279 O -0.636899 1.375904 -0.192027 O -0.839717 -1.331409 -0.125482 C 4.398911 -1.910081 0.078135 H 4.349126 -2.761636 0.766187 H 4.359248 -2.314028 -0.943822 C 4.633042 1.029993 -0.369009 H 4.650337 1.436859 0.651270 H 4.720110 1.877982 -1.057783 C 5.827012 0.084402 -0.583950 H 6.760184 0.622396 -0.379210 H 5.865274 -0.213886 -1.641529 C 5.727946 -1.167967 0.295215 H 6.565860 -1.843990 0.088272 H 5.811634 -0.879786 1.352428 C -2.960272 3.079273 0.200449 C -3.448661 -2.577942 -0.379816 C -3.424916 2.229021 -1.005471 H -4.443048 1.858948 -0.831154 H -2.770741 1.371240 -1.164957 H -3.439422 2.831897 -1.922015 C -3.011278 2.240044 1.500572 H -4.032336 1.875904 1.670488 H -2.723517 2.849283 2.365535 H -2.342820 1.380004 1.455333 C -3.439319 -1.715660 -1.665198 H -3.338833 -2.348436 -2.555824 H -2.620153 -0.994849 -1.657538 H -4.382737 -1.162553 -1.751043 C -3.661088 -1.679978 0.862832 H -3.684519 -2.284613 1.777464 H -4.620646 -1.154096 0.782186 H -2.869600 -0.937335 0.960870 C -4.658974 -3.529280 -0.472942 H -4.757044 -4.165037 0.414970 H -4.613957 -4.174833 -1.358066 H -5.575113 -2.933170 -0.549421 C -3.965866 4.236894 0.362682 H -4.964307 3.819446 0.533498 H -4.024177 4.867150 -0.532861 H -3.728345 4.876982 1.220667 Cl 0.749564 0.206391 2.372007 H -0.923900 -6.565270 -0.197210 H 0.216260 6.536500 -0.320054 Table 8, Entry c Mn 0.481218 -0.043928 0.292441 N 2.054983 1.039771 -0.419545 N 1.845384 -1.489616 0.231372 C 2.010453 2.318755 -0.635710 H 2.925196 2.822195 -0.954808 C 1.613359 -2.764953 0.140763 H 2.469112 -3.440701 0.172097 C 0.871921 3.175812 -0.484376 C -1.230863 4.954808 -0.181046
137
C -0.437230 2.675109 -0.187898 C 1.088322 4.564319 -0.648046 C 0.047227 5.450083 -0.500058 C -1.517967 3.602439 -0.016905 H 2.090670 4.916820 -0.881643 H -2.029062 5.676952 -0.053656 C 0.342604 -3.401632 -0.005044 C -2.049417 -4.755436 -0.345838 C 0.329265 -4.817073 -0.048751 C -0.874331 -2.654451 -0.135073 C -2.109224 -3.366331 -0.322596 C -0.855621 -5.492316 -0.211294 H 1.268844 -5.355927 0.054114 H -2.967555 -5.317064 -0.474807 C 3.291102 0.248225 -0.610951 H 3.245130 -0.181817 -1.624155 C 3.200423 -0.925680 0.388026 H 3.222471 -0.497147 1.399707 O -0.668927 1.380730 -0.117639 O -0.871033 -1.345050 -0.106208 C 4.379310 -1.890284 0.230064 H 4.320505 -2.690675 0.976981 H 4.346812 -2.365265 -0.761262 C 4.617230 1.004123 -0.452483 H 4.633683 1.494320 0.530489 H 4.705860 1.792382 -1.208813 C 5.810530 0.041342 -0.583883 H 6.743443 0.593799 -0.421219 H 5.851783 -0.345602 -1.612085 C 5.706193 -1.132305 0.397284 H 6.545412 -1.822457 0.252745
H 5.781154 -0.757031 1.427059 C -2.935260 3.119359 0.349094 C -3.442135 -2.612606 -0.495540 C -3.490620 2.206128 -0.769829 H -4.502181 1.872376 -0.507182 H -2.866703 1.323528 -0.914802 H -3.552408 2.751208 -1.719874 C -2.899453 2.354074 1.694859 H -3.905443 1.993180 1.943375 H -2.567514 3.011941 2.506566 H -2.225640 1.497504 1.660378 C -3.380217 -1.729538 -1.765763 H -3.232691 -2.346084 -2.661150 H -2.567622 -1.003499 -1.706487 H -4.322807 -1.181514 -1.886234 C -3.725310 -1.734170 0.747859 H -3.778241 -2.350057 1.653514 H -4.689559 -1.224070 0.630380 H -2.951143 -0.979803 0.889352 C -4.634258 -3.577306 -0.662009 H -4.770870 -4.223940 0.212905 H -4.533565 -4.213042 -1.549741 H -5.552584 -2.991757 -0.781250 C -3.921825 4.293144 0.514266 H -4.904520 3.893592 0.787225 H -4.049290 4.866248 -0.412369 H -3.617762 4.984937 1.308864 Cl 0.735973 0.295138 2.616922 H -0.882275 -6.577229 -0.238418 H 0.202145 6.518437 -0.614992
