Supporting Information

Catalytic Ketone Hydrodeoxygenation Mediated by HighlyElectrophilic Phosphonium Cations**Meera Mehta, Michael H. Holthausen, Ian Mallov, Manuel P�rez, Zheng-Wang Qu,Stefan Grimme,* and Douglas W. Stephan*

anie_201502579_sm_miscellaneous_information.pdf

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This PDF file includes:

1. Materials and Methods 4

2. Syntheses and Spectroscopic Data of New Catalysts 5

2.1. Preparation of [(SIMes)PMe2][B(C6F5)4] 5

2.2. Preparation of [(SIMes)PEt2][B(C6F5)4] 6

2.3. Preparation of [(SIMes)PF2Me2][B(C6F5)4] 6

2.4. Preparation of [(SIMes)PF2Et2][B(C6F5)4] 8

2.5. Preparation of [(SIMes)PFMe2][B(C6F5)4]2 (7) 9

2.6. Preparation of [(SIMes)PFEt2][B(C6F5)4]2 (6) 10

2.7. Preparation of [(SIMes)PCl2Ph2][B(C6F5)4] 10

2.8. Preparation of [(SIMes)PClPh2][B(C6F5)4]2 (8) 12

3. Catalytic Hydrodeoxygenation of Ketones 13

3.1. General Procedure for Ketone Hydrosilylation 13

3.2. General Procedure for Ketone Hydrodeoxygenation 13

3.3. Silane Screening Table 14

3.4. Ketone Hydrodeoxygenation Test with B(C6F5)3 14

3.5. Ketone Hydrodeoxygenation Test with [(C6F5)2PPh][B(C6F5)4] (2) 15

3.6. Ketone Hydrodeoxygenation Test with [(C6F5)PPh2][B(C6F5)4] (3) 15

3.7. Ketone Hydrodeoxygenation Test with [PPh3F][B(C6F5)4] (4) 15

3.8. Ketone Hydrodeoxygenation Test with [(SIMes)P(O)Ph2][B(C6F5)4] (9)15

3.9. Characterization Data for Hydrosilylation and Hydrodeoxygenation

Products of Aromatic Ketones 15

3.9.1 Triethyl((2-methylpentan-3-yl)oxy)silane (10b) 15

3.9.2 2-Methylpentane (10c) 16

3.9.3 (Benzyhydryloxy)triethylsilane (11b) 17

3.9.4 Diphenylmethane (11c) 18

3.9.5 1-Benzyl-4-fluorobenzene (12c) 19

3.9.6 1-Benzyl-4-bromobenzene (13c) 20

3.9.7 1-Benzyl-2-chlorobenzene (14c) 21

3.9.8 1-Benzyl-2-methylbenzene (15c) 22

3.9.9 1-Benzyl-4-methoxybenzene (16c) 23

3.9.10 (4-Benzylphenoxy)triethylsilane (16d) 25

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3.9.11. Ethylbenzene (17a) 25

3.9.12. Triethyl(2,2,2-trifluoro-1-phenylethoxy)silane (18b) 26

3.9.13. 1,2-Bis(4-methoxyphenyl)ethane (19c) 27

3.10 Investigation into the Mechanism 29

3.10.1 Hydrodeoxygenation of Benzophenone with HSiPr3 29

3.10.2 Reaction of Catalyst 1 with Acetophenone 29

3.10.3 Reaction of Catalyst 5 with Acetophenone 30

3.11 Characterization Data for Hydrosilylation and

Hydrodeoxygenation Products of Aliphatic Ketones 31

3.11.1. (1-cyclohexylethoxy)triethylsilane (20b) 31

3.11.2. Ethylcyclohexane (20c) 32

3.11.3 Triethyl((3-methylbutan-2-yl)oxy)silane (21b) 33

3.11.4. Isopentane (21c) 34

3.11.5 Triethyl((3-methylpentan-2-yl)oxysilane (22b) 35

3.11.6 3-methylpentane (22c) 36

3.11.7 (1-(Adamantan-1-yl)ethoxy)triethylsilane (23b) 37

3.11.8 Hydrodeoxygenation of 1-Adamanyl methyl ketone 38

3.11.9 ((1-chloropropan-2-yl)oxy)triethylsilane (24b) 39

3.11.10 (Cyclohexyloxy)triethylsilane (25b) 40

3.11.11 Hydodeoxygenation of Cyclohexanone 41

3.11.12 (Heptan-4-yloxy)triethylsilane (26b) 42

3.11.13 Olefin Polymerization of 4-heptanone 43

3.11.14 (Dicyclohexylmethoxy)triethylsilane (27b) 44

3.11.15 Hydrodeoxygenation of Dicyclohexylketone 45

4. Crystallographic Details 46

5. Computational Details 49

5.1 Computational Details 49

5.2 Table S1 50

5.3 Table S2 53

6. Comparing Activity of Catalyst 1, 5, 6, 7 & 8 66

7. References 68

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1. Materials and Methods

General Remarks

All preparations and manipulations were carried out under an anhydrous N2 atmosphere using

standard Schlenk and glovebox techniques. All glassware was oven-dried and cooled under

vacuum before use. Commercial available reagents such as SO2Cl2 (1M, CH2Cl2), XeF2,

Et3SiH, Ph2PCl, B(C6F5)3, ketones and aldehydes were purchased from Sigma Aldrich, Strem

or Apollo Scientific and used without further purification unless indicated otherwise.

[(C6F5)3PF][B(C6F5)4] (1),[1] [(C6F5)2PhPF][B(C6F5)4] (2),[1] [(C6F5)Ph2PF][B(C6F5)4] (3),[2]

[Ph3PF][B(C6F5)4] (4),[3] [Et3Si][B(C6F5)4]*2(C7H8),[4] 1,3-dimesityl-4,5-dihydroimidazol-3-

ium-2-ylidene,[4] [(SIMes)PPh2][B(C6F5)4],[6] and [(SIMes)PFPh2][B(C6F5)4]2 (5),[7] were

prepared following procedures described in literature. CH2Cl2, Et2O, n-pentane, and toluene

were dried using an Innovative Technologies solvent purification system. C6H5F and CD2Cl2

(Aldrich) were deoxygenated, distilled over CaH2, then stored over 4 Å molecular sieves

before use. C6D5Br (Aldrich) was deoxygenated and stored over 4 Å molecular sieves before

use. Reactions were monitored using NMR spectroscopy. NMR spectra were obtained on a

Bruker AvanceIII-400 MHz spectrometer, Varian Agilent DD2 500 MHz spectrometer, and

Varian Agilent DD2 600 MHz spectrometer. Data for 1H NMR spectroscopy is reported as

follows: chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet,

quin = quintet, m = multiplet, dm = doublet of multiplets, b = broad), coupling constant (Hz),

integration. Data for 13C NMR is reported in terms of chemical shift (δ / ppm). High-

resolution mass spectra (HRMS) were obtained on a micro mass 70S-250 spectrometer (EI),

an ABI/Sciex QStar Mass Spectrometer (DART), or on a JOEL AccuTOF-DART (DART).

Mass spectroscopy experiments were run for isolated products and reaction mixtures, however

in some cases the high fragmentation of compounds or volatility did not allow for mass peak

identification.

X-ray Diffraction Studies.

Single crystals were coated with Paratone-N oil, mounted using a glass fibre pin and frozen in

the cold nitrogen stream of the goniometer. Data sets were collected on a Siemens Smart

System CCD diffractometer which was equipped with a rotation anode using graphite-

monochromated MoKα radiation (λ = 0.71073 Å) Data reduction was performed using the

Bruker SMART[8] software package. Data sets were corrected for absorption effects using

SADABS routine (empirical multi-scan method). Structure solutions were found with the

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SHELXS-97 package using the direct method and were refined with SHELXL-97[8] against F2

using first isotropic and anisotropic thermal parameters for all non-hydrogen atoms. Further

details are given in tables in section 4.

2. Syntheses and Spectroscopic Data of New Catalysts

2.1. Preparation of [(SIMes)PMe2][B(C6F5)4]

1,3-Dimesityl-4,5-dihydroimidazol-3-ium-2-ylidene (61 mg, 0.2 mmol,

1.0 eq.) was added portionwise to a solution of Me2PCl (20 mg, 0.2 mmol,

1.0 eq.) giving a yellowish solution. The reaction mixture was stirred at

ambient temperature for ten minutes, then freshly prepared

[Et3Si][B(C6F5)4]*2(C7H8) (196 mg, 0.2 mmol, 1.0 eq.) was added. The reaction mixture was

stirred for another ten minutes, then n-pentane (3 mL) was added which led to the formation

of a colorless precipitate. The supernatant was decanted and the residue was washed with n-

pentane (3 x 3 mL). All volatiles were removed in vacuo giving the respective

imidazolidinium-substituted phosphine salt as colorless, microcrystalline solid (96% yield).

1H NMR (CD2Cl2, 26 °C): δ = 0.80 (6H, d, PCH3, 2JHP = 4.4 Hz); 2.35 (18H, m(br), o/p-

CH3); 4.24 (4H, d, CH2, 4JHP = 2.1 Hz); 7.07 (4H, s, m-Mes); 11B{1H} (CD2Cl2, 26 °C):

δ = −16.7 (s); 13C{1H} (CD2Cl2, 26 °C): δ = 8.6 (2C, d, PCH3, 1JCP = 13.0 Hz); 17.5 (4C, d,

o-CH3, 6JCP = 4.1 Hz); 20.8 (2C, s, p-CH3); 52.3 (2C, d, CH2,

3JCP = 2.2 Hz); 124.1 (4C, s(br),

i-C6F5); 130.5 (4C, s, m-Mes); 130.8 (2C, s, i-Mes); 135.0 (4C, s, o-Mes); 136.2 (8C, d(br),

C6F5, 1JCF = 245 Hz); 138.2 (4C, d(br), C6F5,

1JCF = 239 Hz); 141.8 (2C, s, p-Mes); 148.1

(8C, d(br), C6F5, 1JCF = 243 Hz); 177.4 (1C, d, C-2, 1JCF = 67.1 Hz); 19F{1H} NMR (CD2Cl2,

26 °C): δ = −167.6 (8F, m, m-F); −163.7 (4F, m, p-F); −133.1 (8F, m, o-F); 31P{1H} NMR

(CD2Cl2, 26 °C): δ = −22.7 (s) ppm. Elemental analysis for C47H32BF20N2P: calcd.: C 53.9,

H 3.1, N 2.7; found: C 53.4, H 3.8, N 2.7; ESI MS: m/z: 367.2285 (calcd. for M+: 367.2297).

2.2. Preparation of [(SIMes)PEt2][B(C6F5)4]

1,3-Dimesityl-4,5-dihydroimidazol-3-ium-2-ylidene (61 mg, 0.2 mmol, 1.0 eq.) was added

portionwise to a solution of Et2PCl (24 mg, 0.2 mmol, 1.0 eq.) in C6H5F (3 mL) giving a

yellowish solution. The reaction mixture was stirred at ambient temperature for ten minutes,

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then freshly prepared [Et3Si][B(C6F5)4]*2(C7H8) (196 mg, 0.2 mmol, 1.0 eq.)

was added. The reaction mixture was stirred for another ten minutes, then n-

pentane (3 mL) was added which lead to the formation of a colorless

precipitate. The supernatant was decanted and the residue was washed with n-

pentane (3 x 3 mL). All volatiles were removed in vacuo giving the respective

imidazolidinium-substituted phosphine salt as colorless, microcrystalline solid (96% yield).

1H NMR (CD2Cl2, 26 °C): δ = 0.83 (6H, dt, CH2CH3, 3JHP = 17.3 Hz, 3JHH = 7.5 Hz); 1.08 -

1.12 (2H, m, CH2CH3); 1.25 - 1.37 (2H, m, CH2CH3); 2.35 (6H, s, p-CH3); 2.36 (12H, s, o-

Me); 4.23 (4H, d, NCH2, 4JHP = 1.9 Hz); 7.07 (4H, s, m-H); 11B{1H} (CD2Cl2, 26 °C):

δ = −16.7 (s); 13C{1H} (CD2Cl2, 26 °C): δ = 10.1 (2C, d, CH2CH3, 2JCP = 14.4 Hz); 12.9 (2C,

d, CH2CH3, 1JCP = 14.6 Hz); 17.7 (2C, s, o-Mes); 17.7 (2C, s, o-Mes); 20.8 (2C, s, p-Mes);

52.5 (2C, d, CH2N, 3JCP = 2.2 Hz); 130.5 (4C, s, m-Mes); 131.0 (2C, s, i-Mes); 134.9 (4C, s,

o-Mes); 136.3 (8C, d(br), C6F5, 1JCF = 244 Hz); 138.2 (4C, d(br), C6F5,

1JCF = 241 Hz); 141.7

(2C, s, p-Mes); 148.1 (8C, d(br), C6F5, 1JCF = 241 Hz); 177.0 (1C, d, C-2, 1JCP = 69.6 Hz);

19F{1H} NMR (CD2Cl2, 26 °C): δ = −167.6 (8F, m, m-F); −163.7 (4F, m, p-F); −133.1 (8F,

m, o-F); 31P{1H} NMR (CD2Cl2, 26 °C): δ = 0.67 (s) ppm. Elemental analysis for

C49H36BF20N2P: calcd.: C 54.8, H 3.4, N 2.6; found: C 55.5, H 3.9, N 2.7; ESI MS: m/z:

395.2615 (calcd. for M+: 395.2611).

2.3. Preparation of [(SIMes)PF2Me2][B(C6F5)4]

XeF2 (25 mg, 0.149 mmol, 1.1 eq.) was added portionwise to a solution of

[(SiMes)PMe2][B(C6F5)4] (141 mg, 0.135 mmol, 1.0 eq.) in C6H5F (4 mL).

The reaction mixture turned brownish and was stirred for one hours at

ambient temperature. n-Pentane (3 mL) was added leading to the formation

of a colourless precipitate. The supernatant was removed, the residue was washed with n-

pentane (3 x 3 mL) and dried in vacuo giving [(SiMes)PF2Me2][B(C6F5)4] as colorless,

microcrystalline material (99% yield). Single crystals of [(SiMes)PF2Me2][B(C6F5)4], suitable

for X-ray single crystal structure determination, were obtained by slow diffusion of n-pentane

into a CH2Cl2 solution at −35 °C.

1H NMR (CD2Cl2, 26 °C): δ = 1.06 (6H, dt, PCH3, 2JHP = 16.0 Hz, 3JHF = 12.1 Hz); 2.35 (6H,

s, p-Me); 2.37 (12H, s, o-Me); 4.36 (4H, s, CH2); 7.10 (4H, s, m-H); 11B{1H} (CD2Cl2, 26

°C): δ = −16.6 (s); 13C{1H} (CD2Cl2, 26 °C): δ = 17.4 (4C, t, o-Me, 6JCF = 2.7 Hz); 19.0 (2C,

dt, PCH3, 1JCP = 124.0 Hz, 2JCF = 23.4 Hz); 21.2 (2C, s, p-Me); 52.1 (2C, d, CH2,

3JCP = 7.3 Hz); 124.4 (4C, s(br), i-C6F5); 129.5 (2C, d, i-Mes, 3JCP = 1.5 Hz); 131.0 (4C, s, m-

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Mes); 136.6 (8C, d(br), C6F5, 1JCF = 247 Hz); 136.7 (4C, s, o-Mes); 138.7 (4C, d(br), C6F5,

1JCF = 245 Hz); 143.2 (2C, s, p-Mes); 148.5 (8C, d(br), C6F5, 1JCF = 243 Hz); 165.9 (1C, dt, C-

2, 1JCP = 200.4 Hz, 2JCF = 51.6 Hz); 19F{1H} NMR (CD2Cl2, 26 °C): δ = −167.6 (8F, m, m-

F); −163.7 (4F, m, p-F); −133.0 (8F, m, o-F); −8.9 (2F, d, 1JFP = 643.8 Hz); 31P{1H} NMR

(CD2Cl2, 26 °C): δ = −17.6 (t, 1JPF = 643.8 Hz) ppm. Elemental analysis for C47H32BF22N2P:

calcd.: C 52.1, H 3.0, N 2.6; found: C 51.8, H 3.0, N 2.6; ESI MS: m/z: 405.2263 (calcd. for

M+: 405.2266).

POV-ray Depiction of the cation of [(SiMes)PF2Me2][B(C6F5)4]. C: black, N: blue,

P: orange, F: yellow-green. Hydrogen atoms have been omitted for clarity. Selected

bond distances and angles: C1−N1 1.313(4), C1−N2 1.324(3), P−C1 1.889(3),

P−C4 1.769(4), P−C5 1.795(4), P−F1 1.650(2), P−F2 1.646(2), N1−C1−N2

111.1(3), F1−P−F2 170.9(1), F1−P−C1 84.2(1), F1−P−C4 91.8(2), F1−P−C5

92.4(2), F2−P−C1 86.7(1), F2−P−C4 93.5(2), F2−P−C5 92.0(2), C1−P−C4

121.4(2), C1−P−C5 122.7(1), C4−P−C6 115.8(2).

2.4. Preparation of [(SIMes)PF2Et2][B(C6F5)4]

XeF2 (37 mg, 0.20 mmol, 1.1 eq.) was added portionwise to a solution of

[(SiMes)PEt2][B(C6F5)4] (214 mg, 0.20 mmol, 1.0 eq.) in CH2Cl2 (4 mL).

The reaction mixture turned brownish and was stirred for one hour at ambient

temperature. n-Pentane (3 mL) was added leading to the formation of a

colourless precipitate. The supernatant was removed, the residue was washed with n-pentane

(3 x 3 mL) and dried in vacuo giving [(SiMes)PF2Et2][B(C6F5)4] as colorless, microcrystalline

material (99% yield). Single crystals of [(SiMes)PF2Et2][B(C6F5)4], suitable for X-ray single

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crystals structure determination were obtained by slow diffusion of n-pentane into a CH2Cl2

solution at −35 °C.

1H NMR (CD2Cl2, 26 °C): δ = 0.62 (6H, dtt, CH2CH3, 3JHP = 26.5 Hz, 3JHH = 7.7 Hz,

4JHF = 1.5 Hz); 1.37 (4H, dtt, CH2CH3, 2JHP = 18.1 Hz, 3JHH = 7.7 Hz, 3JHF = 7.7 Hz); 2.36

(6H, s, p-Me); 2.37 (12H, s, o-Me); 4.33 (4H, s, CH2N); 7.10 (4H, s, m-H); 11B{1H} (CD2Cl2,

26 °C): δ = −16.6 (s); 13C{1H} (CD2Cl2, 26 °C): δ = 6.9 (2C, td, CHJCH3, 3JCF = 9.0 Hz,

2JCP = 4.6 Hz); 17.1 (4C, t, o-Mes, 6JCF = 2.7 Hz); 20.8 (2C, s, p-Mes); 24.9 (2C, dt, CH2CH3,

1JCP = 113.2 Hz, 2JCF = 20.1 Hz); 51.7 (2C, d, CH2N, 3JCP = 7.2 Hz); 123.8 (4C, s(br), C6F5);

129.3 (2C, d, i-Mes, 3JCP = 1.2 Hz); 130.5 (4C, s, m-Mes); 136.2 (8C, d(br); C6F5,

1JCF = 244 Hz); 136.3 (4C, s, o-Mes); 138.3 (4C, d(br), C6F5, 1JCF = 247 Hz); 142.6 (2C, s, p-

Mes); 148.1 (8C, d(br), C6F5, 1JCF = 242 Hz); 166.7 (1C, dt, C-2, 1JCP = 194.9 Hz,

2JCF = 54.8 Hz); 19F{1H} NMR (CD2Cl2, 26 °C): δ = −167.6 (8F, m, m-F); −163.7 (4F, m, p-

F); −133.1 (8F, m, o-F); −32.5 (2F, d, 1JFP = 684.5 Hz); 31P{1H} NMR (CD2Cl2, 26 °C):

δ = −17.5 (t, 1JPF = 684.5 Hz) ppm. Elemental analysis for C49H36BF22N2P: calcd.: C 52.9, H

3.3, N 2.5; found: C 52.3, H 3.6, N 2.6; ESI MS: m/z: 433.2579 (calcd. for M+: 433.2579).

POV-ray Depiction of the cation of [(SIMesPF2Et2][B(C6F5)4]. C: black, N: blue,

P: orange, F: yellow-green. Hydrogen atoms have been omitted for clarity. Selected

bond distances and angles: C1−N1 1.319(4), C1−N2 1.315(4), P−C1 1.883(3),

P−C4 1.786(4), P−C10 1.802(4), P−F1 1.659(2), P−F2 1.664(2), N1−C1−N2

111.3(3), F1−P−F2 168.8(1), F1−P−C1 84.2(1), F1−P−C4 92.1(2), F1−P−C6

90.2(2), F2−P−C1 84.6(1), F2−P−C4 93.8(2), F2−P−C6 95.7(2), C1−P−C4

122.1(2), C1−P−C6 121.8(2), C4−P−C6 116.0(2).

2.5. Preparation of [(SIMes)PFMe2][B(C6F5)4]2 (7)

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Freshly prepared [Et3Si][B(C6F5)4]*2(C7H8) (56 mg, 0.057 mmol, 1.0 eq.)

was added to a solution of [(SIMesPF2Me2][B(C6F5)4] (62 mg, 0.057 mmol,

1.0 eq.) in C6D5Br (1 mL). The reaction mixture was stirred for 30 min. at

ambient temperature accompanied by the formation of a yellowish

precipitate. The supernatant was removed, the residue was washed with

CH2Cl2 (3 x 3 mL) and dried in vacuo giving 6 as yellowish powder (80% yield). Compound

6 is only sparingly soluble in non-coordinating, polar solvents (CH2Cl2, C6H5Br, C6H5F).

1H NMR (CD2Cl2, 26 °C): δ = 2.22 (6H, dd, PCH3, 3/2JHF/P = 13.2 Hz, 3/2JHF/P = 12.0 Hz);

2.40 (12H, s, o-Me); 2.43 (6H, s, p-Me); 4.78 (4H, s, CH2N); 7.28 (4H, s, m-H); 11B{1H}

(CD2Cl2, 26 °C): δ = −16.7 (s); 13C{1H} (CD2Cl2, 26 °C): due to the low solubility of 7 a

sufficiently resolved 13C{1H} NMR spectra could not be obtained; 19F{1H} NMR (CD2Cl2,

26 °C): δ = −167.4 (8F, m, m-F); −163.4 (4F, m, p-F); −135.0 (1F, d, 1JFP = 1052.6 Hz);

−133.1 (8F, m, o-F); 31P{1H} NMR (CD2Cl2, 26 °C): δ = 120.7 (d, 1JPF = 1052.6 Hz) ppm.

Elemental analysis for C71H32BF41N2P: calcd.: C 48.9, H 1.9, N 1.6; found: C 48.6, H 2.0, N

1.7; ESI MS: m/z: 307.2 (calcd. for SIMesH+: 307.2), 367.2 (calcd. for

[(SIMesPMe2][B(C6F5)4]: 367.2), 383.2 (calcd. for SIMesP(O)Me2+: 383.2), 405.2 (calcd. for

[(SIMesPF2Me2][B(C6F5)4]: 405.2).

2.6. Preparation of [(SIMes)PFEt2][B(C6F5)4]2 (6)

Freshly prepared [Et3Si][B(C6F5)4]*2(C7H8) (98 mg, 0.10 mmol, 1.0 eq.) was

added to a solution of [(SIMesPF2Et2][B(C6F5)4] (119 mg, 0.10 mmol, 1.0 eq.)

in C6D5Br (2 mL). The reaction mixture was stirred for 30 min. at ambient

temperature accompanied by the formation of a yellowish precipitate. The

supernatant was removed, the residue was washed with CH2Cl2 (3 x 3 mL)

and dried in vacuo giving 6 as yellowish powder (86% yield). Compound 6 is only sparingly

soluble in non-coordinating, polar solvents (CH2Cl2, C6H5Br, C6H5F).

1H NMR (CD2Cl2, 26 °C): δ = 1.39 (6H, dtd, CH2CH3, 3JHP = 24.4 Hz, 3JHH = 8.1 Hz,

4JHF = 0.9 Hz); 2.27 - 2.37 (2H, m, CH2CH3); 2.49 - 2.59 (2H, m., CH2CH3); 2.43 (18H, s,

o/p-Me), 4.77 (4H, s, NCH2); 7.27 (4H, s, m-Mes); 13C{1H} (CD2Cl2, 26 °C, [ppm]): due to

the low solubility of [(SiMes)PFEt2][B(C6F5)4]2 a sufficiently resolved 13C{1H} NMR spectra

could not be obtained; 19F{1H} NMR (CD2Cl2, 26 °C): δ = −167.4 (8F, m, m-F); −163.3 (4F,

m, p-F); −152.9 (1F, d, 1JFP = 1055.8 Hz); −133.1 (8F, m, o-F); 31P{1H} NMR (CD2Cl2,

26 °C): δ = 126.6 (d, 1JPF = 1055.8 Hz) ppm. Elemental analysis for C73H36BF41N2P: calcd.:

9

C 49.5, H 2.1, N 1.6; found: C 49.3, H 2.6, N 1.7; ESI MS: m/z: 307.2173 (calcd. for

SIMesH+: 307.2169), 411.2560 (calcd. for [(SiMes)POMe2]+: 411.2560), 433.2576 (calcd. for

[(SiMes)PFMe2]2++e−: 433.2579).

2.7. Preparation of [(SIMes)PCl2Ph2][B(C6F5)4]

0.11 mL SO2Cl2 solution (1.0M in CH2Cl2, 0.11 mmol, 1 eq.) was added to a

solution of [(SIMes)PPh2][B(C6F5)4] (129 mg, 0.11 mmol, 1.0 eq.) in

C6D5Br (1 mL). Upon standing for 30 min a colourless microcrystalline solid

precipitated from the yellow solution. The supernatant was decanted and the

residue was washed with toluene (2 x 2 mL) and pentane (2 x 2 mL) and

dried in vacuo yielding [(SIMes)PCl2Ph2][B(C6F5)4] as colourless solid (131 mg, 96% yield).

Single crystals of [(SIMes)PCl2Ph2][B(C6F5)4], suitable for X-ray single crystal structure

determination, were obtained by cooling a saturated CH2Cl2 solution at −35 oC. While NMR

data assignable to [(SIMes)PCl2Ph2][B(C6F5)4] was obtained, even in the case where the

product was purified by multiple recrystallizations notable amounts of Ph2PCl and

[(SIMes)PPh2][B(C6F5)4] were observed in solution, indicating some decomposition of

the product.

1H NMR (CD2Cl2, 26 °C): δ = 2.31 (12H, s, o-Me); 2.35 (6H, s, p-Me); 4.55 (4H, s(br),

CH2), 7.09 (4H, s, m-H); 7.43 (4H, m, Ph); 7.60-7.81 (4H, m, Ph); 7.99 (2H, m, Ph); 11B{1H}

(CD2Cl2, 26 °C): δ = −16.7 (s); 13C{1H} (CD2Cl2, 26 °C): δ = 19.0 (4C, d, o-CH3, 3JCP = 4.4

Hz); 21.6 (2C, s, p-Me); 51.5 (2C, s, CH2); 125.9 (2C, d, i-Ph, 1JCP = 2.5 Hz,); 129.6 (2C, d,

m-Mes, 3JCP = 10.6 Hz); 129.5 (4C, d, m-Ph, 3JCP = 6.7 Hz); 131.3 (4C, s, m-Mes); 131.3 (2C,

s, p-Ph); 132.4 (4C, d, o-Ph, 2JCP = 24.5 Hz); 135.7 (4C, s, o-Mes); 136.2 (8C, d(br); C6F5,

1JCF = 244 Hz); 138.1 (4C, d(br), C6F5, 1JCF = 247 Hz); 143.2 (2C, s, p-Mes); 148.9 (8C, d(br),

C6F5, 1JCF = 241 Hz); 158.9 (1C, s, C2); 19F{1H} NMR (CD2Cl2, 26 °C): δ = −167.6 (8F, m,

m-F); −163.7 (4F, t, p-F); −133.1, (8F, m, o-F); 31P{1H} NMR (CD2Cl2, 26 °C): δ = −63.9 (s)

ppm. Elemental analysis for C57H36BF20Cl2N2P: calcd.: C 55.1, H 2.9, N 2.3; found: C 54.4,

H 3.2, N 2.4; ESI MS: m/z: 561.2 (calcd. for M+: 561.2).

10

POV-ray depiction of the cation of [(SiMes)PCl2Ph2][B(C6F5)4]. C: black, N: blue,

P: orange, Cl: green. Hydrogen atoms have been omitted for clarity. Selected bond

distances and angles: C1−N1 1.330(3), C1−N2 1.321(3), P−C1 1.888(2), P−C4

1.845(2), P−C10 1.829(2), P−Cl1 2.198(1), P−Cl2 2.187(1), N1−C1−N2 112.3(2),

Cl1−P−Cl2 164.7(1), Cl1−P−C1 81.9(1), Cl1−P−C4 96.5(1), Cl1−P−C10 91.2(1),

Cl2−P−C1 84.7(1), Cl2−P−C4 96.6(1), Cl2−P−C10 91.7(1), C1−P−C4 120.1(1),

C1−P−C10 129.6(1), C4−P−C10 110.3(1).

2.8. Preparation of [(SIMes)PClPh2][B(C6F5)4]2 (8)

Freshly prepared [Et3Si][B(C6F5)4]*2(C7H8) (98 mg, 0.11 mmol, 1.0 eq.) was

added portionwise to a suspension of [(SIMes)PCl2Ph2][B(C6F5)4] (137 mg,

0.11 mmol, 1.0 eq.) in 2 mL toluene. The reaction mixture was stirred for two

hours at ambient temperature giving a yellow solid and a yellowish

supernatant. The supernatant was decanted and the residue was washed with

toluene (2 x 2 mL) and pentane (2 x 2 mL) and dried in vacuo yielding 8 as a yellow solid

(116 mg, 60% yield).

1H NMR (CD2Cl2, 26 °C): δ = 2.21 (12H, s, o-Me); 2.24 (6H, s, o-Me); 4.60 (4H, s, CH2);

6.81 (4H, s, m-H); 7.59 (4H, m, o-Ph), 7.67 (4H, td, m-Ph); 8.00 (2H, tt, p-Ph, 3JHH = 7.5 Hz,

4JHH = 1.5 Hz ); 11B{1H} (CD2Cl2, 26 °C): δ = −16.7 (s); 13C{1H} (CD2Cl2, 26 °C): δ = 19.1

(4C, s, o-Me); 21.4 (2C, s, p-Me); 55.5 (2C, d, CH2, 3JCP = 4.7 Hz); 111.2 (2C, d, i-Ph,

1JCP = 91.2 Hz); 126.0 (2C, s, i-Mes); 132.0 (4C, s, m-Mes); 132.6 (4C, d, m-Ph,

3JCP = 13.7 Hz); 133.3 (4C, d, o-Ph, 2JCP = 14.1 Hz); 135.2 (4C, s, o-Mes); 137.1 (8C, d(br);

C6F5, 1JCF = 241 Hz); 139.0 (4C, d(br), C6F5,

1JCF = 244 Hz); 140.7 (2C, d, p-Ph, 4JCP = 3.6 Hz

); 145.6 (2C, s, p-Mes); 149.0 (8C, d(br), C6F5, 1JCF = 241 Hz); 155.5 (1C, d, C2,

11

1JCP = 86.5 Hz); 19F{1H} NMR (CD2Cl2, 26 °C): δ = −167.3 (8F, m, m-F); −163.4 (4F, m, p-

F); −133.1, (8F, m, o-F); 31P{1H} NMR (CD2Cl2, 26 °C, [ppm]): δ = 47.4 ppm. Elemental

analysis for C81H36B2F41N2P: calcd.: C 51.6, H 1.9, N 1.5; found: C 52.4, H 2.3, N 1.5; ESI

MS: m/z: 263.2 (calcd. for M+: 263.2).

POV-ray depiction of the dication of [(SiMes)PClPh2][B(C6F5)4]. C: black, N:

blue, P: orange, Cl: green. Hydrogen atoms have been omitted for clarity. Selected

bond distances and angles: C1−N1 1.320(4), C1−N2 1.324(4), P−C1 1.870(3), ),

P−C22 1.776(3), P−C28 1.771(3), P−Cl 1.972(2), N1−C1−N2 112.9(3), Cl1−P−C1

105.1(1), Cl1−P−C22 106.1(2), Cl1−P−C28 109.9(1), C1−P−C22 112.4(2),

C1−P−C28 107.6(2), C22−P−C28 115.29(16)

12

3. Catalytic Hydrodeoxygenation of Ketones

3.1. General Procedure for Ketone Hydrosilylation

All reactions were carried out under identical conditions on a 0.1 - 0.2 mmol scale. In a glove

box, the respective catalyst (1 mol%, 1: 2 mg, 7: 2 mg, 6: 2 mg, 8: 2 mg) was added to a

solution of Et3SiH in CD2Cl2 (0.7 mL). The respective substrate (1: 0.16 mmol , 7:

0.11 mmol, 6: 0.11 mmol, 8: 0.11 mmol) was then added in one equivalence. The reaction

mixture was transferred to a NMR tube, sealed and monitored by 1H NMR, 13C NMR and 29Si

NMR. For aromatic ketone 18a once equivalence of Et3SiH and lead to cleanly yield

hydrosilylated product 18b. For most aliphatic ketone substrates the hydrosilylated

intermediates were obtained by using three equivalent of Et3SiH and leaving the reaction at

room temperature for 1 hour. The hydrosilylated product were isolated by removing the

excess silane and solvent under reduced pressure, dissolving in pentane and filtration over a

silica plug. For substrate 25a two equivalence was sufficient to isolate the hydrosilylated

product 25b. For substrate 26a more than one equivalence of silane lead to a mixture of

products, however with one equivalence the hydrosilylated product 26b could be isolated.

3.2. General Procedure for Ketone Hydrodeoxygenation

All reactions were carried out under identical conditions on a 0.1 - 0.2 mmol scale. In a glove

box, the respective catalyst (1 mol%, 1: 2 mg, 7: 2 mg, 6: 2 mg, 8: 2 mg) was added to a

solution of Et3SiH (0.23 – 0.48 mmol, 2.1 – 3.0 eq.) in CD2Cl2 (0.7 mL). The respective

substrate (1: 0.16 mmol , 7: 0.11 mmol, 6: 0.11 mmol, 8: 0.11 mmol) was then added in one

equivalence. The reaction mixture was transferred to a NMR tube, sealed and monitored by

1H NMR and 13C NMR spectroscopy. The bis(triethylsilyl) ether was identified by a 29Si

NMR resonance at 8.88 ppm. In most cases, with 3.1 equivalents Et3SiH, complete

hydrodeoxygenation of ketones was obtained. For examples where the hydrodeoxygenation

product has a low boiling point, an internal standard of toluene was added to determine degree

of conversion. For less volatile products, reaction mixtures were worked-up by evaporating

the di(triethylsilyl) ether by-product. To avoid loss of product under reduced pressure the

solution was occasionally monitored by 1H NMR. For the substrates that could not be isolated,

NMR data for the crude reaction mixture is presented, in which the bis(triethylsilyl) ether by-

product can be observed. Upon completion of catalysis, 31P NMR reveals that the

13

[(SIMes)PFPh2][B(C6F5)4]2 (5) catalyst decomposes to [(SIMes)POPh2][B(C6F5)4], observed

as a peak at 14.1 ppm, and [(SIMes)PF2Ph2][B(C6F5)], observed as a peak as a triplet at -62.9

ppm (1JPF = 735 Hz). Catalyst [(C6F5)3PF][B(C6F5)4] (1) decomposes to [OP C6F5)3], and

[C6F5)3PF2] observed in the 31P NMR as a singlet at -8.29 and a triplet -47.99 ppm

consecutively. Routinely, catalytic runs were monitored by 11B and 19F NMR spectroscopy.

According to the NMR data, decomposition of borate anion does not occur for any catalysts

used.

3.3 Silane Screening Table

To a solution of catalyst 5 (2 mg) and 2.1 equivalence of silane (0.23 mmol) in CD2Cl2

benzophenone (0.11 mmol) was added and the reaction monitored by 1H NMR and 13C NMR.

Series of silanes were investigated, 1H NMR for iPr3SiH can be found in section 3.10.1 when

discussing the mechanism.

Silane Time Conversion

Et3SiH 5 >99

iPr3SiH 5 11

Ph3SiH 5 >99

PMHS 5 >99

(EtO)2SiH 5 >99

Me2HSi-O-SiHMe2 5 >99

3.4 Ketone Hydrodeoxygenation Test with B(C6F5)3

Catalyst B(C6F5)3 (1 mol%, 2 mg) was dissolved in CD2Cl2 (0.7 mL). Triethylsilane (125 µL,

0.82 mmol, 2.1 eq.) was added with a micro-syringe. Benzophenone (71 mg, 0.39 mmol,

1.0 eq.) was added and the reaction mixture was monitored by 1H NMR spectroscopy for

24 h. For higher catalyst loadings of B(C6F5)3 the same protocol was used.

14

3.5 Ketone Hydrodeoxygenation Test with [(C6F5)2PFPh][B(C6F5)4] (2)

Catalyst [(C6F5)2PPh][B(C6F5)4] (2) (1 mol%, 2 mg) was dissolved in CD2Cl2 (0.7 mL).

Triethylsilane (59 µL, 0.37 mmol, 2.1 eq.) was added with a micro-syringe. Benzophenone

(32 mg, 0.18 mmol, 1.0 eq.) was added and the reaction mixture was monitored by 1H NMR

spectroscopy for 24 h.

3.6 Ketone Hydrodeoxygenation Test with [(C6F5)PFPh2][B(C6F5)4] (3)

Catalyst [(SIMes)P(O)Ph2][B(C6F5)4] (3) (1 mol%, 2 mg) was dissolved in CD2Cl2 (0.7 mL).

Triethylsilane (116 µL, 0.76 mmol, 2.1 eq.) was added with a micro-syringe. Benzophenone

(66 mg, 0.36 mmol, 1.0 eq.) was added and the reaction mixture was monitored by 1H NMR

spectroscopy for 24 h.

3.7 Ketone Hydrodeoxygenation Test with [FPPh3][B(C6F5)4] (4)

Catalyst [Ph3PF][B(C6F5)4] (4) (1 mol%, 2 mg) was dissolved in CD2Cl2 (0.7 mL).

Triethylsilane (67 µL, 0.44 mmol, 2.0 eq.) was added with a micro-syringe. Benzophenone

(38 mg, 0.21 mmol, 1.0 eq.) was added and the reaction mixture was monitored by 1H NMR

spectroscopy for 24 h.

3.8 Ketone Hydrodeoxygenation Test with [(SIMes)P(O)Ph2][B(C6F5)4] (9)

Catalyst [(SIMes)P(O)Ph2][B(C6F5)4] (9) (1mol%, 2 mg) was dissolved in CD2Cl2 (0.7 mL).

Triethylsilane (54 µL, 0.35 mmol, 2.1 eq.) was added with a micro-syringe. Benzophenone

(31 mg, 0.17 mmol, 1.0 eq.) was added and the reaction mixture was monitored by 1H NMR

spectroscopy for 24 h.

3.9 Characterization Data for Hydrosilyaltion and Hydrodeoxygenation

Products of Aromatic Ketones

3.9.1. Triethyl((2-methylpentan-3-yl)oxy)silane (10b)

1H NMR (400 MHz, CD2Cl2): δ = 3.41 (q, 3JHH = 4Hz, 1H); 1.71 (m, 1H);

1.42 (m, 2H); 0.97 (m, 3JHH = 8 Hz, 9H); 0.86 (CH3, m, 9H); 0.61 (q, 3JHH = 8

15

Hz, 6H); 13C NMR (101 MHz, CD2Cl2): δ = 78.7; 33.0; 26.7; 18.6; 18.0; 10.2; 7.4; 5.8; 29Si

NMR (119 MHz, CD2Cl2): δ = 15.2 ppm.

3.9.2. 2-Methylpentane (10c)9

1H NMR (400 MHz, CD2Cl2): δ = 1.55 (m, 1H); 1.30 (m, 2H); 1.17 (m, 2H),

0.88 (d, 3JHH = 6.8 Hz 6H); 0.87 (m, 3H overlapping d); 13C{1H} NMR (100

MHz, CD2Cl2): δ = 42.0; 28.3; 23.0; 21.8; 14.7.

16

3.9.3. (Benzyhydryloxy)triethylsilane (11b)10

1H NMR (400 MHz, CD2Cl2): δ = 7.45 (m, 4H); 7.35 (m, 4H); 7.26 (m,

2H); 5.85 (s, 1H); 0.96 (t, 3JHH = 8Hz, 9H); 0.66 (q, 3JHH = 8Hz, 6H); 13C

NMR (100 MHz, CD2Cl2): δ = 146.1; 128.8; 127.6; 126.8; 77.0; 7.2; 5.5;

29Si NMR (126 MHz, CD2Cl2): δ = 20.1 (s) ppm. DART MS: m/z: 316.21017 (calcd. for

M+NH4+: 316.20967).

17

3.9.4. Diphenylmethane (11c)11

1H NMR (500 MHz, CD2Cl2): δ = 7.29 (m, 4H); 7.20 (m, 6H); 3.98 (s,

2H); 13C{1H} NMR (126 MHz, CD2Cl2): δ = 141.4; 128.8; 128.4; 126.0;

41.9 ppm. DART MS: m/z: 186.12872 (calcd. for M+NH4+: 186.12827).

18

3.9.5. 1-Benzyl-4-fluorobenzene (12c)11,12

1H NMR (500 MHz, CD2Cl2): δ = 7.30 (m, 2H); 7.20 (m, 5H); 7.00 (m,

2H); 3.97 (s, 2H); 13C NMR (126 MHz, CD2Cl2): δ = 162.0 (d, 1JCF =

243.1 Hz); 141.8; 137.8; 130.9; 129.3 (d, 2JCF = 34.1 Hz); 126.8; 115.7 (d, 3JCF = 21.1 Hz);

41.6; 19F NMR (376 MHz, CD2Cl2): δ = −118.1 (s) ppm.

19

3.9.6. 1-Benzyl-4-bromobenzene (13c)13

1H NMR (500 MHz, CD2Cl2): δ = 7.42 (m, 2H); 7.30 (m, 2H); 7.22

(m, 1H); 7.18 (m, 2H); 7.10 (m, 2H); 3.94 (s, 2H); 13C NMR (126

MHz, CD2Cl2): δ = 141.2; 141.1; 132.0; 131.2; 129.4; 129.1; 126.8; 120.3; 41.8 ppm.

20

3.9.7. 1-Benzyl-2-chlorobenzene (14c)11

1H NMR (500 MHz, CD2Cl2): δ = 7.40 (m, 1H); 7.30 (m, 2H); 7.22 (m,

6H); 4.13 (s, 2H); 13C NMR (126 MHz, CD2Cl2): δ = 140.3; 139.4; 134.7;

131.7; 130.1; 129.5; 129.0; 128.3; 127.5; 126.8; 39.7 ppm. DART MS:

m/z: 220.08995 (calcd. for M+NH4+: 220.08930).

21

3.9.8. 1-Benzyl-2-methylbenzene (15c)11

1H NMR (500 MHz, CD2Cl2): δ = 7.30 (m, 2H); 7.17 (m, 7H); 4.02 (s,

2H); 2.28 (s, 3H); 13C NMR (126 MHz, CD2Cl2): δ = 141.3; 139.8; 137.2;

130.8; 130.5; 129.3; 129.0; 127.0; 126.6; 126.5; 40.0; 20.0 ppm. DART

MS: m/z: 200.14314 (calcd. for M+NH4+: 200.14392).

22

3.9.9. 1-Benzyl-4-methoxybenzene (16c)14

Isolated Yield = 73%. 1H NMR (500 MHz, CD2Cl2): δ = 7.28 (m,

2H); 7.19 (m, 3H); 7.12 (m, 2H); 6.84 (m, 2H); 3.92 (s, 2H); 3.77 (s,

3H); 13C NMR (126 MHz, CD2Cl2): δ = 158.9; 142.7; 134.2; 130.5; 129.5; 129.2; 126.7;

114.6; 55.7; 41.5 ppm. DART MS: m/z: 216.13914 (calcd. for M+NH4+: 216.13884).

23

24

3.9.10. (4-Benzylphenoxy)triethylsilane (16d)15

Isolated Yield = 60%. 1H NMR (500 MHz, CD2Cl2): δ = 7.27

(m, 2H); 7.18 (m, 3H); 7.06 (m, 2H); 6.75 (m, 2H); 3.90 (s, 2H);

0.94 (t, 3JHH = 7.9 Hz, 9H); 0.54 (q, 3JHH = 7.9 Hz, 6H); 13C NMR

(126 MHz, CD2Cl2): δ = 154.6; 142.4; 134.1; 130.5; 129.3; 129.0; 126.5; 115.7; 41.5; 7.2,

6.9; 29Si NMR (119 MHz, CD2Cl2): δ = −37.0 (s) ppm. DART MS: m/z: 184.1 (calcd. for

M+NH4+: 184.1).

3.9.11. Ethylbenzene (17c)16

1H NMR (400 MHz, CD2Cl2): δ = 7.26 (m, 5H); 2.70 (q, 3JHH = 8 Hz, 2H); 1.29

25

(t, 3JHH = 8 Hz, 3H); 13C NMR (100 MHz, CD2Cl2): δ = 145.1; 129.7; 128.9; 126.2; 29.6;

16.2 ppm.

3.9.12. Triethyl(2,2,2-trifluoro-1-phenylethoxy)silane (18b)10

Isolated yield: 74%; 1H NMR (500 MHz, CD2Cl2): δ = 7.47 (m, 2H); 7.37

(m, 3H); 4.97 (q, 2JHF = 6.7 Hz, 1H); 0.90 (t, 3JHH = 7.9 Hz, 9H); 0.61 (q,

3JHH = 7.9 Hz, 6H); 13C NMR (126 MHz, CD2Cl2): δ = 136.1; 129.7; 128.8;

128.2; 125.0 (q, 1JCF = 282.3 Hz); 73.9 (q, 2JCF = 31.8 Hz); 6.7, 5.0; 19F NMR (564 MHz,

CD2Cl2): δ = −78.8 (d, 3JHF = 7.2 Hz); 29Si NMR (119 MHz, CD2Cl2): δ = 24.6 (s) ppm.

DART MS: m/z: 308.16629 (calcd. for M+NH4+: 308.165751).

26

3.9.13. 1,2-Bis(4-methoxyphenyl)ethane (19c)17

Isolated Yield = 35%.i 1H NMR (500 MHz, CD2Cl2):

δ = 7.08 (m, 4H); 6.80 (m, 4H); 3.76 (s, 6H); 2.82 (s, 4H);

13C NMR (126 MHz, CD2Cl2): δ = 158.4; 134.5; 129.9;

114.1; 55.7; 37.7 ppm. DART MS: m/z: 260.16538 (calcd.

for M+NH4+: 260.16505).

27

28

3.10. Investigation into the Mechanism of Hydrodeoxygenation

3.10.1 Hydrodeoxygenation of Benzophenone with HSii-Pr3

Catalyst (5) (1 mol%, 2 mg) was dissolved in CD2Cl2 (0.7 mL). Triisopropylsilane (44 µL,

0.76 mmol, 2.1 eq.) was added with a micro-syringe. Benzophenone (20 mg, 0.36 mmol,

1.0 eq.) was added and the reaction mixture was monitored by 1H NMR spectroscopy for

48 h. The analogous reaction with triethylsilane goes to completion within 5 hours.

3.10.2 Reaction of Catalyst 1 with Acetophenone

Catalyst (1) (10 mg) was dissolved in CD2Cl2 (0.7 mL), an excess of acetophenone was

added. The solution was allowed to sit for an hour, before 31P NMR was run. The 1H NMR

revealed a mixture of products and the organic decomposition product could not be identified.

29

3.10.3 Reaction of Catalyst 5 with Acetophenone

Catalyst (5) (10 mg) was dissolved in CD2Cl2 (0.7 mL), an excess of acetophenone was

added. The solution was allowed to sit for an hour, before 31P NMR was run. The 1H NMR

revealed a mixture of products and the organic decomposition product could not be identified.

30

3.11. Characterization Data for Hydrosilylation and Hydrodeoxygenation

Products of Aliphatic Ketones

3.11.1. (1-cyclohexylethoxy)triethylsilane (20b)

Isolated Yield: 84%; 1H NMR (500 MHz, CD2Cl2): δ = 3.56 (p, J= 5 Hz,

1H); 1.84 (m, 1H); 1.76 (m, 2H); 1.66 (m, 2H); 1.32-0.96 (m, 6H); 0.92 (t,

3JHH = 7.9 Hz, 9H); 0.51 (q, 3JHH = 7.9 Hz, 6H); 13C{1H} NMR (126 MHz,

CD2Cl2): δ = 73.07; 46.37; 29.37; 29.28; 27.38; 27.08; 27.06; 21.17; 7.33; 5.62; 29Si NMR

(79.5 MHz, CD2Cl2) δ: 15.4 (s) ppm. DART MS: m/z: 243.21399 (calcd. for M+H+:

243.214418).

31

3.11.2. Ethylcyclohexane (20c)

1H NMR (400 MHz, CD2Cl2): δ = 1.73 (m, 4H); 1.21 (m, 5H); 0.89 (t, 3JHH = 8

Hz, 3H); 0.63 (m, 4H). 13C NMR (100 MHz, CD2Cl2): δ = 40.22; 33.72; 30.78;

27.48; 27.16; 11.84.

32

3.11.3. Triethylsilyl((3-methylbutan-2-yl)oxy)silane (21b)

1H NMR (500 MHz, CD2Cl2): δ = 3.57 (m, 1H); 1.58 (m, 1H); 1.09 (dd,

3JHH = 31.0, 6.2 Hz, 3H); 0.93 (m, 15H); 0.53 (m, 6H); 13C NMR (126 MHz,

CD2Cl2): δ = 73.5; 36.1; 35.6; 20.6; 20.4; 18.5; 18.3; 18.2; 7.3; 5.6; 29Si NMR

(79.5 MHz, CD2Cl2): δ = 14.9 ppm.

33

3.11.4. Isopentane (21c)

1H NMR (400 MHz, CD2Cl2): δ = 1.48 (m, 1H); 1.24 (m, 2H); (d, 3JHH = 8Hz,

9H); 13C NMR (100 MHz, CD2Cl2): δ = 32.29; 30.47; 22.64; 12.11 ppm.

34

3.11.5. Triethyl((3-methylpentan-2-yl)oxysilane (22b)

Isolated Yield: 77%; 1H NMR (500 MHz, CD2Cl2): δ = 3.71 (m, 1H); 1.52

(m, 2H); 1.11 (m, 1H); 1.05 (dd, 3JHH = 17.1, 6.2 Hz, 3H); 0.96 (m, 9H);

0.89 (t, 3JHH = 7.4 Hz, 3H); 0.84 (dd, 3JHH = 6.8, 2.5 Hz, 3H); 0.56 (m,

6H); 13C NMR (126 MHz, CD2Cl2): δ = 72.2 (2C); 43.0; 42.9; 26.2; 25.6; 20.9; 19.7; 14.7;

14.1; 12.4; 12.3; 7.31; 7.20; 6.99; 5.64; 5.60; 29Si NMR (79.5 MHz, CD2Cl2) δ: 15.4(s);

15.2(s) ppm. DART MS: m/z: 217.19867 (calcd. for M+H+: 217.198768).

35

3.11.6. 3-methylpentane (22c)9

1H NMR (400 MHz, CD2Cl2): δ = 1.37 (m, 1H); 1.16 (m, 4H); 1.02 (d, 3JHH =

8Hz, 3H); 0.89 (t, 3JHH = 8Hz, 6H). 13C NMR (100 MHz, CD2Cl2): δ = 36.8;

29.8; 21.8; 11.9 ppm.

36

3.11.7. (1-(Adamantan-1-yl)ethoxy)triethylsilane (23b)

Isolated Yield = 72%. 1H NMR (500 MHz, CD2Cl2): δ = 3.28 (m, 1H); 1.96

(m, 3H); 1.57 (m, 12H); 1.03 (d, 3JHH = 4Hz, 3H); 0.96 (m, 9H); 0.60 (m, 6H);

13C NMR (126 MHz, CD2Cl2): δ = 76.7; 38.7; 38.3; 29.3; 17.5; 7.4; 5.8; 29Si

NMR (79.5 MHz, CD2Cl2): δ = 15.5 ppm.

37

3.11.8. Hydrodeoxygenation of 1-adamanyl methyl ketone

38

3.11.9. ((1-chloropropan-2-yl)oxy)triethylsilane (24b)

1H NMR (400 MHz, CD2Cl2): δ = 3.99 (m, 1H); 3.45 (m, 2H); 1.24 (d,

3JHH = 4 Hz, 3H); 0.99 (m, 9H); 0.62 (m, 6H); 13C NMR (100 MHz, CD2Cl2): δ =

69.27; 51.01; 21.99; 8.55; 7.15 ppm.

39

3.11.10. (Cyclohexyloxy)triethylsilane (25b)

Isolated Yield = 84%; 1H NMR (400 MHz, C6D6): δ = 0.60 (m, 6H); 1.02 (m,

9H), 1.09 - 1.83 (m, 10H); 3.62 (m, 1H); 13C{1H} (126 MHz, C6D6): δ = 5.5; 7.3;

24.4; 26.1; 36.5; 70.7; 29Si{1H} (76.5 MHz, C6D6): δ = 15.1 (s) ppm. DART MS

m/z: 215.1838 (calcd. for MH+: 215.1826).

40

3.11.11. Hydrodeoxygenation of Cyclohexanone

41

3.11.12. (Heptan-4-yloxy)triethylsilane (26b)

Isolated Yield = 83%. 1H NMR (400 MHz, CD2Cl2) δ: 3.67 (m, 1H); 1.39

(m, 8H); 0.93 (t, 3JHH = 8.0 Hz, 15H); 0.52 (q, 3JHH = 8.0 Hz, 6H); 13C

NMR (100 MHz, CD2Cl2) δ: 72.7; 40.2; 19.2; 14.7; 7.3; 5.6; 29Si NMR (79.5 MHz, CD2Cl2)

δ: 14.9 (s) ppm. HRMS (DART Ionization, m/z): calcd. for C13H31OSi, [M+H+]: 231,21442;

found: 231.21496.

42

3.11.13. Olefin Polymerization of 4-heptanone18

43

3.11.14. (Dicyclohexylmethoxy)triethylsilane (27b)19

1H NMR (500 MHz, CD2Cl2) δ: 3.19 (t, 3JHH = 5.1 Hz, 1H); 1.75 (m, 6H);

1.61 (m, 5H); 1.43 (m, 2H); 1.17 (m, 9H); 0.99 (m, 9H); 0.64 (q, 3JHH = 8

Hz, 6H); 13C NMR (126 MHz, CD2Cl2) δ:82.6; 41.9; 31.4; 28.9; 27.2; 7.7;

6.3; 29Si NMR (79.5 MHz, CD2Cl2) δ: 4.3 (s) ppm.

44

3.11.15. Hydrodeoxygenation of Dicyclohexylketone

45

4. Crystallographic Details

Crystallographic data and details of the structure refinements of compounds

[(SIMes)PF2Me2][B(C6F5)4]*0.63(CH2Cl2), [(SIMes)PF2Me2][B(C6F5)4]*0.63(CH2Cl2) and

[(SIMes)PF2Me2][B(C6F5)4]*0.88(CH2Cl2).

[(SIMes)PF2Me2][B(C6

F5)4]*0.63(CH2Cl2)

[(SIMes)PF2Et2][B(C6F

5)4]*0.63(CH2Cl2)

[(SIMes)PCl2Ph2][B(C6F5)

4]*0.88(CH2Cl2)

formula C47.8H34.5BCl1.3F22N2P C49.6H37.3BCl1.3F22N2P C57.9H37.8BCl3.8F20N2P

Mr [g mol1] 1140.37 1165.66 1315.87

color, habit block, colorless block, colorless block, colorless

crystal system monoclinic Tetragonal monoclinic

Space group P21/c P41212 P21/c

a [Å] 18.064(2) 18.00(1) 17.339(1)

b [Å] 17.896(2) 18.00(1) 18.911(1)

c [Å] 16.749(2) 30.61(1) 16.851(1)

[°] 90 90 90

[°] 115.463(4) 90 99.768(3)

[°] 90 90 90

V [Å3] 4888(1) 9913(4) 5445(1)

Z 4 8 4

T [K] 149(2) 149(2) 149(2)

Crystal size [mm] 0.19x0.12x0.10 0.17x0.14x0.07 0.20x0.10x0.10

c [g cm3] 1.549 1.562 1.605

F(000) 2297 4706 2651

min [°]

max [°]

1.69

27.2

1.31

27.56

1.61

27.52

Index range

23 h 23

23 k 20

21 l 21

23 h 23

19 k 23

28 l 39

22 h 20

24 k 24

21 l 21

[mm1] 0.246 0.245 0.347

absorption correction SADABS SADABS SADABS

reflections collected 42970 89317 90885

46

reflections unique 11256 11435 12477

Rint 0.0544 0.0975 0.0417

reflection obs.

[F>3(F)] 6885 7585 9187

residual density

[e Å3]

0.433

–0.620

0.663

–0.290

0.521

–0.460

parameters 666 692 755

GOOF 1.031 0.974 1.043

R1 [I>2(I)] 0.0616 0.0560 0.0477

wR2 (all data) 0.1846 0.1329 0.1124

CCDC 1062018 1062019 1062020

Crystallographic data and details of the structure refinements of compound [(SIMes)PClPh2][B(C6F5)4].

[(SIMes)PClPh2]

[B(C6F5)4]

formula C87H41B2BrCl1F40N2P

Mr [g mol1] 2042.17

color, habit block, yellow

crystal system orthorhombic

Space group P b c a

a [Å] 22.0939(9)

b [Å] 18.0209(7)

c [Å] 40.661(3)

[°] 90

[°] 90

[°] 90

V [Å3] 16189.3(1)

Z 8

T [K] 149(2)

Crystal size [mm] 0.50x020x0.20

c [g cm3] 1.676

F(000) 8112

min [°]

max [°]

1.36

27.51

Index range

28 h 28

23 k 22

51 l 52

[mm1] 0.703

absorption correction SADABS

reflections collected 127490

reflections unique 18564

Rint 0.0790

reflection obs.

[F>3(F)] 11228

residual density

[e Å3]

2.222

–1.469

parameters 1201

GOOF 0.992

R1 [I>2(I)] 0.0582

wR2 (all data) 0.1667

CCDC 1062021

47

48

5. Calculation Details

5.1 Calculation Details

The quantum chemical DFT calculations have been performed with the TURBOMOLE 6.4

suite of programs.[24] The structures are fully optimized at the TPSS-D3/def2-TZVP +

COSMO level of theory, which combines the TPSS meta-GGA density functional[25] with the

BJ-damped DFT-D3 dispersion correction[26] and the def2-TZVP basis set,[27] using the

Conductor-like Screening Model (COSMO) continuum solvation model[28] for CH2Cl2 solvent

(dielectric constant = 8.93, refractive constant n = 1.424, Rsolv = 2.94 Å). For the present

(C6F5)3PF+ + O=CPhMe + 2Et3SiH hydrosilylation/deoxygenation reaction system with 92

atoms, it leads to 2064 basis functions (35, 23, 217 atoms and 1091, 319, 2327 basis

functions, respectively) in our DFT calculations. The density-fitting RI-J approach[29] is used

to accelerate the geometry optimization and numerical harmonic frequency calculations in

solution. The optimized structures are characterized by frequency analysis to identify the

nature of located stationary points (no imaginary frequency for true minima and only one

imaginary frequency for transition state) and to provide thermal corrections according to a

modified ideal gasrigid rotorharmonic oscillator model. [30]

The final solvation energies in CH2Cl2 solvent are computed with the COSMO-RS

solvation model (parameter file: BP_TZVP_C30_1201.ctd) in the COSMOtherm program

package[31] on the above TPSS-D3 optimized structures. To check the effects of the chosen

DFT functional on the reaction energies and barriers, gas-phase single-point calculations

using the TPSS-D3, hybrid PW6B95-D3[32] and double-hybrid B2PLYP-D3[33] are performed

using a larger def2-QZVP basis set.[34] It leads to 4545 basis functions (35, 23, 217 atoms

and 2008, 753, 2892 basis functions, respectively) in our single-point calculations. The final

reaction enthalpies (H) and Gibbs free energies (G) are determined from the gas-phase

single-point energies plus thermal corrections plus COSMO-RS solvation energies. The

results from different DFT functionals are in good mutual agreement, especially between the

higher level PW6B95-D3 and B2PLYP-D3 results with a standard deviation of 2.1 kcal/mol.

In our discussion, the final B2PLYP-D3 Gibbs free energies (in kcal/mol, at 298.15 K and 1

atm standard state) will be used unless specified otherwise. The unit cell of

[(SIMes)PMe2F2][B(C6F5)4], [(SIMes)PEt2F2][B(C6F5)4] and

[(SIMes)PPh2Cl2][B(C6F5)4] contain 5 molecules CH2Cl2 which have been treated as a

diffuse contribution to the overall scattering without specific atom positions by

49

SQUEEZE/PLATON due to their high degree of disorder. One of the ethyl-groups of

[(SIMes)PEt2F2][B(C6F5)4] is disordered over two positions with an s.o.f. of 0.69

5.2 Table S1

The TPSS-D3 computed lowest imaginary frequency (Imfrq), zero-point energies (ZPE), gas-

phase enthalpic (Hc) and Gibbs free-energy (Gc) corrections; the COSMO-RS computed

solvation enthalpic (Hsol) and Gibbs free-energy (Gsol) corrections in CH2Cl2 solution; the

B2PLYP-D3, TPSS-D3 and PW6B95-D3 single-point energies; the relative electronic

energies (Ee), Gibbs free-energies (G) and enthalpies (H) at the B2PLYP-D3 level; the

differences of relative electronic energies at the TPSS-D3 and PW6B95-D3 levels with

respect to B2PLYP-D3. Each structure is labeled either by its molecular formula or a specific

name in bold. Each transition structure (with only one imaginary frequency) are indicated by

the "TS" prefix, followed by the names of two connected structures. For example, the

50

Table S1. The TPSS-D3 computed lowest imaginary frequency (Imfrq), zero-point energies (ZPE), gas-phase enthalpic (Hc) and Gibbs free-energy (Gc) corrections; the COSMO-RS computed

solvation enthalpic (Hsol) and Gibbs free-energy (Gsol) corrections in CH2Cl2 solution; the B2PLYP-D3, TPSS-D3 and PW6B95-D3 single-point energies; the relative electronic energies (Ee),

Gibbs free-energies (G) and enthalpies (H) at the B2PLYP-D3 level; the differences of relative electronic energies at the TPSS-D3 and PW6B95-D3 levels with respect to B2PLYP-D3. Each

structure is labeled either by its molecular formula or a specific name in bold. Each transition structure (with only one imaginary frequency) are indicated by the "TS" prefix, followed by the names

of two connected structures. For example, the transition structure between A and B is labeled as TSAB.

Species ImFrq ZPE Hc Gc Hsol Gsol B2PLYP-D3 TPSS-D3 Pw6B95-D3 Ee G H (T-B) (P-B)

cm-1 kcal/mol kcal/mol kcal/mol kcal/mol kcal/mol Eh Eh Eh kcal/mol kcal/mol kcal/mol kcal/mol kcal/mol

1 0.0 95.13 115.12 58.86 -53.43 -43.89 -2624.456753 -2625.797085 -2628.373805 -- -- -- -- --

HSiEt3 0.0 127.45 134.99 105.37 -7.10 0.22 -527.689881 -528.006473 -528.487371 -- -- -- -- --

17a 0.0 85.21 90.69 65.05 -14.05 -4.94 -384.840960 -385.147022 -385.559663 -- -- -- -- --

17b 0.0 216.07 229.10 187.68 -15.34 -5.98 -912.593704 -913.209751 -914.107435 -- -- -- -- --

17c 0.0 96.98 102.13 77.36 -9.80 -2.33 -310.813856 -311.085732 -311.423845 -- -- -- -- --

1H 0.0 100.48 120.64 64.35 -16.16 -8.50 -2625.292084 -2626.635051 -2629.214657 -- -- -- -- --

O(SiEt3)2 0.0 247.83 263.57 216.91 -10.74 -2.27 -1129.547409 -1130.203300 -1131.249027 -- -- -- -- --

A 0.0 223.33 251.43 180.01 -50.61 -40.49 -3152.172934 -3153.827239 -3156.890411 -- -- -- -- --

B 0.0 209.46 222.54 180.92 -51.92 -40.75 -911.751290 -912.370168 -913.264803 -- -- -- -- --

C 0.0 341.73 361.67 307.33 -50.41 -38.62 -1439.488426 -1440.421563 -1441.803010 -- -- -- -- --

B·HSiEt3 -53.1 337.35 357.97 301.49 -51.08 -39.09 -1439.445942 -1440.381111 -1441.755258 -- -- -- -- --

C·1H 0.0 442.31 483.62 386.67 -59.96 -47.28 -4064.803028 -4067.073769 -4071.032712 -- -- -- -- --

TSAB -65.7 308.78 341.71 261.15 -55.13 -43.29 -3537.021776 -3538.984477 -3542.458501 -- -- -- -- --

TSAC -173.0 440.71 481.39 386.35 -55.95 -43.52 -4064.763168 -4067.036708 -4070.997750 -- -- -- -- --

TSBC -115.5 338.86 358.72 303.99 -52.18 -40.16 -1439.441727 -1440.373346 -1441.751991 -- -- -- -- --

TSC1 -98.6 438.67 479.82 383.19 -58.59 -46.10 -4064.801033 -4067.065669 -4071.020038 -- -- -- -- --

1_HSiEt3_17a 0.0 307.79 340.80 229.29 -74.59 -48.61 -3536.987594 -3538.950580 -3542.420838 0.0 0.0 0.0 0.0 0.0

A_17a 0.0 308.54 342.12 245.06 -64.66 -45.44 -3537.013894 -3538.974261 -3542.450074 -16.5 2.4 -5.3 1.7 -1.9

TSAB -65.7 308.78 341.71 261.15 -55.13 -43.29 -3537.021776 -3538.984477 -3542.458501 -21.5 15.7 -1.1 0.2 -2.2

B_1H 0.0 309.94 343.18 245.27 -68.08 -49.24 -3537.043374 -3539.005219 -3542.479460 -35.0 -19.7 -26.1 0.7 -1.8

TSB1 -641.5 308.90 341.99 261.43 -54.98 -43.74 -3537.046183 -3539.005851 -3542.477283 -36.8 0.2 -16.0 2.1 1.3

1_17b 0.0 311.20 344.22 246.54 -68.77 -49.87 -3537.050457 -3539.006836 -3542.481240 -39.5 -23.5 -30.2 4.2 1.5

1_HSiEt3_17b 0.0 438.65 479.21 351.92 -75.87 -49.65 -4064.740338 -4067.013309 -4070.968610 0.0 0.0 0.0 0.0 0.0

A_17b 0.0 439.40 480.52 367.69 -65.94 -46.48 -4064.766639 -4067.036990 -4070.997846 -16.5 2.4 -5.3 1.7 -1.9

51

TSAC -173.0 440.71 481.39 386.35 -55.95 -43.52 -4064.763168 -4067.036708 -4070.997750 -14.3 26.2 7.8 -0.4 -4.0

C_1H 0.0 442.21 482.31 371.68 -66.57 -47.12 -4064.780510 -4067.056613 -4071.017666 -25.2 -2.9 -12.8 -2.0 -5.6

C·1H 0.0 442.31 483.62 386.67 -59.96 -47.28 -4064.803028 -4067.073769 -4071.032712 -39.3 -2.2 -19.0 1.4 -0.9

TSC1 -98.6 438.67 479.82 383.19 -58.59 -46.10 -4064.801033 -4067.065669 -4071.020038 -38.1 -3.3 -20.2 5.2 5.8

1_O(SiEt3)2_17c 0.0 439.95 480.82 353.13 -73.97 -48.49 -4064.818018 -4067.086116 -4071.046676 -48.8 -46.4 -45.2 3.0 -0.2

B_HSiEt3 0.0 336.91 357.53 286.29 -59.02 -40.53 -1439.441171 -1440.376641 -1441.752174 0.0 0.0 0.0 0.0 0.0

B·HSiEt3 -53.1 337.35 357.97 301.49 -51.08 -39.09 -1439.445942 -1440.381111 -1441.755258 -3.0 13.6 5.4 0.2 1.1

TSBC -115.5 338.86 358.72 303.99 -52.18 -40.16 -1439.441727 -1440.373346 -1441.751991 -0.4 17.7 7.7 2.4 0.5

C 0.0 341.73 361.67 307.33 -50.41 -38.62 -1439.488426 -1440.421563 -1441.803010 -29.7 -6.7 -16.9 1.5 -2.2

O(SiEt3)2_HCPhMe+ 0.0 338.02 358.74 287.69 -65.33 -47.20 -1439.470889 -1440.401046 -1441.780164 -18.7 -23.9 -23.8 3.3 1.1

52

5.3 Table S2

The TPSS-D3 optimized atomic Cartesian coordinates (in Å). Each structure is labeled either

by its molecular formula or a name in bold, followed by the molecular charge, the number of

atoms, the total energy, and the detailed atomic coordinates.

Table S2. The TPSS-D3 optimized atomic Cartesian coordinates (in Å). Each structure is labeled by the specific name,

followed by the molecular charge, the number of atoms, the total energy, and the detailed atomic coordinates.

1.xyz charge = +1

35

Energy = -2625.727531057

P -0.0020064 0.0013454 0.7559933

C 0.6183793 1.5896905 0.2876910

C 1.8311717 2.0180771 0.8620739

C -0.0149657 2.4512475 -0.6270209

C 2.3845970 3.2519169 0.5654602

C 0.5288860 3.6907013 -0.9370123

C 1.7257485 4.0903524 -0.3389906

C -1.6868283 -0.2570626 0.2855839

C -2.6655462 0.5793110 0.8572862

C -2.1152912 -1.2426052 -0.6229077

C -4.0110351 0.4357861 0.5644912

C -3.4608311 -1.3975925 -0.9287095

C -4.4067521 -0.5608814 -0.3328962

C 1.0646295 -1.3282950 0.2854910

C 0.8310327 -2.5942534 0.8572719

C 2.1295831 -1.2067778 -0.6263472

C 1.6266336 -3.6879104 0.5614582

C 2.9350216 -2.2948059 -0.9353431

C 2.6845557 -3.5325771 -0.3395831

F -0.0032647 0.0000917 2.3175909

F -2.2815786 1.5537859 1.6930167

F -4.9195453 1.2355147 1.1184432

F -5.6896996 -0.7090749 -0.6240351

F -3.8520619 -2.3383687 -1.7864361

F -1.2404903 -2.0564663 -1.2235440

F -0.2030081 -2.7493465 1.6951992

F 1.3893504 -4.8747248 1.1155544

F 3.4524931 -4.5699232 -0.6343268

F 3.9424197 -2.1633703 -1.7964987

F 2.3951667 -0.0423892 -1.2280541

F 2.4781139 1.1999112 1.7033104

F 3.5306032 3.6381514 1.1217466

F 2.2443941 5.2719971 -0.6345291

F -0.0839386 4.4977592 -1.8011945

F -1.1559366 2.1007858 -1.2302333

HSiEt3.xyz charge = 0

23

Energy = -527.9786970961

H 1.9799650 0.8208108 0.0000000

Si 0.6740488 0.0900614 0.0000000

C 0.6686097 -0.2031789 2.8744463

C 0.6686097 -0.2031789 -2.8744463

C 0.5955014 -0.9878120 1.5504478

C 0.5955014 -0.9878120 -1.5504478

C -0.7099310 1.3787930 0.0000000

C -2.1269355 0.7723348 0.0000000

H -0.1723463 0.4927328 2.9706057

H -0.1723463 0.4927328 -2.9706057

H -0.3304674 -1.5795992 -1.5192190

H -0.3304674 -1.5795992 1.5192190

H 0.6439729 -0.8740024 3.7411678

H 0.6439729 -0.8740024 -3.7411678

H -0.5832405 2.0299261 -0.8759316

H -0.5832405 2.0299261 0.8759316

H 1.4180391 -1.7151659 1.5013325

H 1.4180391 -1.7151659 -1.5013325

H 1.5912478 0.3855938 2.9353869

H 1.5912478 0.3855938 -2.9353869

H -2.2911112 0.1445828 -0.8832961

H -2.2911112 0.1445828 0.8832961

H -2.8975586 1.5518459 0.0000000

17a.xyz charge = 0

17

Energy = -385.1326479387

O 1.6862089 -0.9287819 -1.6107153

C 1.4438737 -0.1935126 -0.6531764

C 2.5347888 0.6553387 -0.0376731

C 0.0675880 -0.1230433 -0.0787637

C -0.2401889 0.7057385 1.0117649

C -0.9463622 -0.9102794 -0.6491520

C -1.5371489 0.7460911 1.5214868

C -2.2398844 -0.8697515 -0.1402729

C -2.5376036 -0.0406850 0.9468574

H 2.6632900 0.4087721 1.0224433

H 2.2728851 1.7181136 -0.0944803

H 3.4701192 0.4800529 -0.5704271

H 0.5297280 1.3211691 1.4659757

H -0.6964713 -1.5470819 -1.4920819

H -1.7673164 1.3897609 2.3653736

H -3.0189006 -1.4811811 -0.5864443

H -3.5480783 -0.0088272 1.3444702

17b.xyz charge = 0

40

Energy = -913.1619006118

Si -1.7427623 0.2901632 0.0387335

O -0.6494424 -0.9026730 0.4758367

C -3.4443017 -1.5864313 -1.3467776

C -2.6753262 -0.2606340 -1.5064493

C -2.8809879 0.4098365 1.5304673

C -0.1437652 2.1028756 -1.6073781

C -2.1744713 0.8406179 2.8311229

C -0.9133169 1.9570066 -0.2802226

C 1.8575596 0.0847373 1.2790830

C 1.7154059 -0.5196947 0.0272751

C 0.6699918 -2.8055733 -0.1291668

C 3.0255226 0.7783898 1.6016941

C 2.7622176 -0.4204055 -0.8970399

C 4.0661152 0.8732599 0.6757698

C 3.9311542 0.2700752 -0.5772996

H -3.9367668 -1.8822917 -2.2804484

H -3.3667549 0.5441783 -1.7964727

H -2.7701732 -2.3984620 -1.0523531

H -4.2172438 -1.5066061 -0.5744310

H -3.6891810 1.1161024 1.2914145

H -0.7907109 1.8999426 -2.4678672

H -1.7148714 1.8298010 2.7260123

H -1.9607951 -0.3470029 -2.3377183

H 0.7023158 1.4099246 -1.6535120

H -2.8753723 0.8882105 3.6727595

H -1.7111927 2.7144871 -0.2376287

H -3.3640800 -0.5656513 1.6777915

H 0.2566359 3.1166636 -1.7254006

H -1.3808891 0.1336051 3.0956083

H -0.2434552 2.1795193 0.5613058

H 1.0418906 0.0179660 1.9918744

H -0.2308051 -3.3511475 -0.4268711

H 3.1217008 1.2483815 2.5770356

H 1.5153970 -3.1623073 -0.7259179

H 0.8762356 -3.0059875 0.9267832

H 2.6569616 -0.8786295 -1.8785547

H 4.9729800 1.4171316 0.9254027

H 4.7324001 0.3447816 -1.3076828

C 0.4645293 -1.3032720 -0.3328265

H 0.2389156 -1.1207319 -1.3947502

17c.xyz charge = 0

18

Energy = -311.0695897443

C -0.2668948 1.2034139 -0.1906070

C 0.4372865 0.0001894 -0.3347756

C 2.7430386 -0.0004904 0.7112271

C -1.6341066 1.2066161 0.0916488

C -0.2665915 -1.2031168 -0.1897745

C -2.3229499 0.0000436 0.2354284

C -1.6337959 -1.2064595 0.0925201

H 0.2620403 2.1473929 -0.3054556

H 2.5112209 0.8850125 1.3129195

H 2.5116468 -0.8870626 1.3115027

H 3.8174246 -0.0000471 0.4973217

H -2.1625095 2.1508104 0.1949969

H 0.2625020 -2.1470638 -0.3041518

H -3.3876858 -0.0000206 0.4518437

H -2.1619669 -2.1507001 0.1965992

C 1.9262564 0.0003252 -0.5944215

H 2.1935985 0.8832561 -1.1868321

H 2.1936037 -0.8818650 -1.1879433

1H.xyz charge = 0

36

Energy = -2626.514695615

P 0.0021892 -0.0004270 -0.0538759

F 0.0024973 -0.0008077 -1.7431967

H 0.0030283 -0.0001540 1.3741053

C 1.1093618 -1.4535482 -0.0641592

C 0.7934348 -2.5635413 0.7222464

C 2.3079361 -1.4981738 -0.7797973

C 1.6101714 -3.6859771 0.7829588

C 3.1558406 -2.5995693 -0.7178632

C 2.8013470 -3.6992070 0.0603601

C 0.7037365 1.6865025 -0.0653422

C 0.1413463 2.7439273 -0.7841729

C 1.8212976 1.9726582 0.7218920

C 0.6678956 4.0304439 -0.7245766

C 2.3813896 3.2429652 0.7806603

C 1.7959021 4.2779234 0.0544316

C -1.8095427 -0.2337527 -0.0638843

C -2.6129543 0.5874044 0.7304990

C -2.4475823 -1.2435161 -0.7882295

C -3.9933454 0.4401288 0.7903688

C -3.8254810 -1.4271213 -0.7285694

C -4.6004697 -0.5774537 0.0574854

F -2.0500983 1.5818440 1.4472857

F -4.7399064 1.2638555 1.5406522

F -5.9263995 -0.7407879 0.1120701

F -4.4119448 -2.4186761 -1.4159731

F -1.7362671 -2.1058560 -1.5355877

F -0.3547307 -2.5761696 1.4301907

F 1.2630782 -4.7480016 1.5248232

F 3.6058979 -4.7656678 0.1171644

F 4.3134761 -2.6079522 -1.3956979

F 2.7035261 -0.4480490 -1.5206871

F -0.9647956 2.5574363 -1.5257863

F 0.0946279 5.0340161 -1.4057229

F 2.3144461 5.5092128 0.1086238

F 3.4729196 3.4782531 1.5237313

F 2.4081719 0.9878374 1.4327128

O(SiEt3)2.xyz charge = 0

45

Energy = -1130.142621008

Si -0.3728699 1.7299258 0.5892280

Si -1.9173155 -1.1019800 -0.0310223

O -1.1414654 0.3121958 0.2780592

C -2.5452390 3.1504965 -0.6627572

C -1.0097470 3.0297681 -0.6189101

C -0.7514801 2.2362309 2.3654233

C 1.8593075 0.8331865 -0.9956775

C -0.4798419 1.1330833 3.4063368

C 1.4790305 1.4639311 0.3577822

C -1.7384561 -0.5527842 -2.8537155

C -2.7087774 -0.9865380 -1.7379486

C -0.6499550 -2.4968546 0.0173991

C -4.1789262 -0.1565736 1.4837411

C 0.2095058 -2.5208035 1.2962384

C -3.2357755 -1.3599667 1.2920919

H -2.8710180 3.9071569 -1.3860860

H -3.0037023 2.1972386 -0.9461229

H -2.9513640 3.4306529 0.3158018

H -0.5639909 3.9994181 -0.3523791

H -0.6309526 2.7913564 -1.6229560

H -0.1598058 3.1323124 2.6039564

H -1.8040810 2.5472843 2.4256455

H 1.3756623 -0.1411673 -1.1219079

H 2.9418963 0.6837745 -1.0826493

H 1.5435606 1.4658461 -1.8330146

H -0.7238842 1.4665440 4.4217849

H -1.0778063 0.2406484 3.1941333

H 0.5733139 0.8300474 3.4009400

H 1.9873684 2.4319253 0.4774438

H 1.8470604 0.8285294 1.1759183

H -0.9087044 -1.2610623 -2.9580733

H -2.2427036 -0.4868387 -3.8249261

H -1.3048022 0.4284392 -2.6341975

H -3.1500665 -1.9639890 -1.9824648

H -3.5506412 -0.2814153 -1.6879563

H 0.0028669 -2.4090869 -0.8626314

H -1.1807265 -3.4534777 -0.0965458

H -4.7249676 0.0732485 0.5617457

H -3.6155279 0.7402743 1.7620931

H -4.9197406 -0.3444732 2.2697495

H 0.7606652 -1.5818414 1.4134248

H -0.4103894 -2.6498954 2.1908203

H 0.9396918 -3.3383134 1.2778467

H -3.8180789 -2.2562649 1.0324319

H -2.7376026 -1.5916139 2.2443323

A.xyz charge = +1

58

Energy = -3153.722590366

P 0.0098889 0.0055534 -1.3279901

H -0.0107152 -0.0053997 1.2752335

Si -0.0301937 -0.0104423 2.7912921

F 0.0187434 0.0139921 -2.8964226

C -1.0535101 -1.3563625 -0.9235673

C -2.3447454 -1.3610096 -1.4837516

C -0.6885915 -2.4506700 -0.1203426

C -3.2422377 -2.3907218 -1.2505472

C -1.5767648 -3.4886411 0.1259202

C -2.8534636 -3.4586713 -0.4377640

C 1.7149111 -0.2394248 -0.9019665

C 2.3664092 -1.3582669 -1.4544211

C 2.4723717 0.6174728 -0.0850683

C 3.7012779 -1.6295259 -1.1998010

C 3.8092945 0.3579107 0.1835088

C 4.4235455 -0.7654556 -0.3727810

C -0.6382884 1.6030272 -0.9068586

C 0.0108569 2.7299497 -1.4453204

C -1.7748536 1.8256785 -0.1105482

C -0.4303877 4.0197978 -1.1962560

C -2.2278817 3.1112579 0.1517841

C -1.5556653 4.2083157 -0.3897231

F 1.6732100 -2.2000316 -2.2329342

F 4.2926466 -2.6964044 -1.7326040

F 5.6995892 -1.0119306 -0.1158801

F 4.5065813 1.1748500 0.9731821

F 1.9307854 1.7083943 0.4657148

F 1.1007359 2.5558975 -2.2051233

F 0.2047845 5.0681575 -1.7154995

F -1.9886084 5.4347606 -0.1378325

F -3.2988941 3.3009251 0.9224870

F -2.4556013 0.8083976 0.4266704

F -2.7293293 -0.3303970 -2.2489075

F -4.4588867 -2.3678924 -1.7903525

F -3.7006466 -4.4491230 -0.2003668

F -1.2162598 -4.5100926 0.9028422

F 0.5224464 -2.5268726 0.4398749

C -1.0625098 -1.4892002 3.3404225

C -2.5596860 -1.4287149 2.9830033

H -0.9511230 -1.5619100 4.4319851

H -0.6129961 -2.4085843 2.9429845

H -3.0836199 -2.3288358 3.3217143

H -3.0454784 -0.5662410 3.4495989

H -2.7149701 -1.3405525 1.9023973

C 1.7542518 -0.1606744 3.3803715

C 2.4580431 -1.4900495 3.0483615

H 1.7383258 -0.0190930 4.4707416

H 2.3337802 0.6853084 2.9881714

H 3.4918104 -1.4908865 3.4099794

H 1.9438555 -2.3384250 3.5103963

H 2.4830193 -1.6770011 1.9694850

C -0.8039054 1.6139968 3.3535817

C 0.0028597 2.8852629 3.0280041

H -0.9402571 1.5375765 4.4420054

H -1.8183664 1.6903518 2.9408957

H -0.5225664 3.7844368 3.3669928

H 0.9826228 2.8696623 3.5150788

H 0.1795473 2.9887781 1.9521290

B.xyz charge = +1

39

Energy = -912.3752846643

Si 1.9441253 -0.2727907 -0.0687224

O 0.1708480 -0.1881110 -0.1016162

C -0.7158777 0.7173510 0.1144811

C 3.2681185 2.2837585 -0.5310448

C 2.6308416 1.0541836 -1.2074467

C 2.4123831 -0.0899387 1.7339203

C 1.6423663 -2.1923604 -2.1771000

C 1.6382042 -1.0057189 2.7024270

C 2.1688540 -1.9976667 -0.7404606

C -2.4044654 -1.0494258 -0.2205479

C -2.0941550 0.3092022 0.0326153

C -0.2744002 2.1069900 0.4041832

C -3.7246330 -1.4527805 -0.3136239

C -3.1417894 1.2457716 0.1867065

C -4.7541103 -0.5131223 -0.1635451

C -4.4617767 0.8319493 0.0831984

H 3.6726925 2.9676836 -1.2837299

H 3.3888550 0.5477848 -1.8217427

H 2.5462676 2.8453793 0.0699779

H 4.0892683 1.9891778 0.1295815

H 3.4884862 -0.3134417 1.7844885

H 2.1471198 -1.5234198 -2.8819675

H 1.7554927 -2.0605827 2.4352544

H 1.8496611 1.3630721 -1.9149397

H 0.5675477 -1.9901699 -2.2371745

H 1.9997866 -0.8774111 3.7272576

H 3.2431452 -2.2255414 -0.6993667

H 2.3199393 0.9588130 2.0440874

H 1.8079455 -3.2199297 -2.5157157

H 0.5669040 -0.7778628 2.6977797

H 1.6821707 -2.7082919 -0.0594730

H -1.5995092 -1.7663586 -0.3333150

H 0.5931582 2.0867018 1.0698820

H -3.9630485 -2.4941216 -0.5020467

H 0.0412832 2.5706094 -0.5396833

H -1.0551426 2.7206897 0.8470241

H -2.9256163 2.2900972 0.3775235

H -5.7888141 -0.8335526 -0.2376590

H -5.2648046 1.5521303 0.1972385

C.xyz charge = +1

62

Energy = -1440.391942116

Si 0.1643567 1.4652749 0.7007679

Si -1.6754087 -1.1039743 -0.1633407

O -0.2454470 -0.0003384 -0.2940255

C -1.6175547 2.9992474 -0.9512203

C -1.2974125 2.6156872 0.5061117

C 0.5295945 0.9541548 2.4664916

C 2.9984426 2.1804790 0.7622783

C -0.5929876 0.6774439 3.4800019

C 1.6746723 2.3417273 -0.0078085

C 3.1632198 -0.1619511 -1.7170571

C 2.0895551 -0.6455559 -0.9610267

C 0.4317784 0.3611675 -2.6682084

C 4.4755572 -0.3938068 -1.3053908

C 2.3537239 -1.3684369 0.2099658

C 4.7297974 -1.1055619 -0.1329137

C 3.6635786 -1.5902894 0.6277899

C 0.6739260 -0.4967926 -1.4471294

C -1.8523652 -2.3030659 -2.8667477

C -2.4601544 -1.3165669 -1.8529281

C -1.0149127 -2.7350944 0.4785918

C -4.0934764 0.4264023 0.3723562

C -0.6888251 -2.8158435 1.9813371

C -2.9192043 -0.3416313 1.0118269

H -2.4122697 3.7504633 -0.9906003

H -0.7410271 3.4150592 -1.4589638

H -1.9534668 2.1323113 -1.5299893

H -2.1938912 2.2469661 1.0106896

H -0.9967786 3.5160993 1.0637150

H 1.2561489 0.1316021 2.4552286

H 1.1040046 1.8239365 2.8226035

H 2.9154977 2.5705242 1.7809713

H 3.7961996 2.7351476 0.2586439

H 3.3052687 1.1341797 0.8252409

H -0.1805162 0.6328342 4.4929625

H -1.3504449 1.4680608 3.4666371

H -1.0929212 -0.2749402 3.2913821

H 1.8336389 2.1079706 -1.0623150

H 1.3766019 3.4012415 0.0084457

H 2.9846452 0.3925895 -2.6319718

H -0.6350596 0.4168447 -2.8858985

H 0.8202622 1.3739049 -2.5551802

H 0.9264962 -0.1053928 -3.5251752

H 5.2986046 -0.0127501 -1.9018966

H 1.5316012 -1.7592078 0.7984331

H 5.7519699 -1.2804704 0.1882368

H 3.8516432 -2.1454502 1.5415976

H 0.2661289 -1.4973285 -1.6205752

H -1.6178042 -3.2641407 -2.3983182

H -2.5597203 -2.4935722 -3.6795992

H -0.9352920 -1.9189347 -3.3222799

H -3.4588739 -1.6876947 -1.5709864

H -2.6511495 -0.3408450 -2.3172318

H -0.1541940 -3.0655911 -0.1171588

H -1.8127981 -3.4564738 0.2443063

H -4.6947670 -0.2303676 -0.2622759

H -3.7547118 1.2619701 -0.2461440

H -4.7494193 0.8299819 1.1497971

H 0.0974154 -2.1112212 2.2711642

H -1.5699568 -2.5918420 2.5900683

H -0.3462891 -3.8201757 2.2478894

H -3.3174023 -1.2022978 1.5695890

H -2.4278271 0.2743337 1.7692359

B·HSiEt3.xyz charge = +1

62

Energy = -1440.351528999

H -0.9640341 -0.3864964 -0.4952874

Si 2.5856900 0.1035591 0.1489922

O 0.8825910 0.2786694 0.1650680

C -0.1156732 0.5325827 -0.7116461

C 2.3327714 -0.3268495 2.9847610

C 3.0072667 0.5581233 1.9181128

C 3.0873430 -1.6757002 -0.1924396

C 2.8979692 2.7679673 -0.9318015

C 3.1158520 -2.1561219 -1.6544887

C 3.3363444 1.2987133 -1.0873899

C -0.5749693 2.5110603 0.7713765

C -0.8921600 1.7792169 -0.3786828

C 0.1863376 0.2887934 -2.1802642

C -1.2919674 3.6623900 1.0902888

C -1.9391647 2.2131452 -1.2034196

C -2.3366102 4.0880235 0.2686846

C -2.6575857 3.3612870 -0.8805913

H 2.6138227 -0.0128422 3.9954498

H 1.2414978 -0.2691481 2.9113219

H 2.6196946 -1.3780120 2.8722451

H 4.0999559 0.5033644 2.0235409

H 2.7419921 1.6107845 2.0858139

H 4.0992217 -1.7655515 0.2315876

H 2.4626817 -2.3440443 0.4145413

H 3.1183363 3.1456864 0.0719700

H 1.8213269 2.8865762 -1.0956445

H 3.4151229 3.4106130 -1.6517247

H 3.7523751 -1.5154773 -2.2729389

H 3.5034467 -3.1779654 -1.7228105

H 2.1175091 -2.1590928 -2.1039508

H 4.4259034 1.2210365 -0.9534464

H 3.1457829 0.9515081 -2.1109204

H 0.2393655 2.1800132 1.4051025

H 0.6769622 -0.6765536 -2.3153930

H -0.7229264 0.3092757 -2.7827013

H 0.8486030 1.0835304 -2.5353621

H -1.0340347 4.2269786 1.9808799

H -2.2010808 1.6604082 -2.0998941

H -2.8976518 4.9829402 0.5200586

H -3.4661768 3.6892902 -1.5263238

Si -1.9964265 -1.5133275 0.2177251

C -0.7191211 -2.6883465 0.8947612

C -0.1623983 -3.7084144 -0.1147391

H -1.1994181 -3.2053317 1.7389444

H 0.0860112 -2.0889408 1.3395832

H 0.5922155 -4.3432834 0.3591655

H -0.9540027 -4.3586285 -0.4980530

H 0.3068994 -3.2149338 -0.9709941

C -2.9607627 -2.0844343 -1.2724468

C -4.0272202 -1.1134737 -1.8102467

H -3.4352813 -3.0234961 -0.9439211

H -2.2570656 -2.3763616 -2.0622242

H -4.5889358 -1.5814206 -2.6238858

H -4.7391155 -0.8280658 -1.0300431

H -3.5744665 -0.1983345 -2.2020456

C -2.8676766 -0.4070370 1.4364013

C -2.1017889 -0.1453257 2.7467934

H -3.8327793 -0.8934408 1.6449314

H -3.1174065 0.5365392 0.9332446

H -2.6853080 0.5062481 3.4037588

H -1.9040131 -1.0770791 3.2849780

H -1.1436704 0.3452065 2.5556388

C·1H.xyz charge = +1

98

Energy = -4066.918795511

P -2.4642482 0.1679971 -0.4806482

H -1.0906360 0.0398088 -0.0914848

Si 4.5675070 -0.9785543 1.6953282

O 3.4853255 0.1164420 0.7161666

C 1.9393701 -0.1594564 0.6222578

C -1.2797320 2.6688436 -0.8503814

C -1.3388594 4.0013984 -2.8446460

C -2.0972278 3.0131816 -3.4692690

C -3.5889234 0.6873146 3.9941750

C -2.0568006 1.6680282 -1.4381757

C -2.8438287 -0.4142100 3.5768963

C -0.9283982 3.8315189 -1.5233960

C -4.0163497 1.6309112 3.0620467

C -2.5336442 -0.5483440 2.2295752

C -2.9542509 0.3711007 1.2680384

C -3.7050284 1.4611605 1.7162194

C -2.4526960 1.8668864 -2.7635945

C -1.4161477 -1.7474730 -2.2296596

C -2.3857506 -1.4820190 -1.2620293

C -1.2971323 -2.9908470 -2.8368391

C -2.1411047 -4.0247858 -2.4368356

C -3.2321973 -2.5303719 -0.8980763

C -3.1074833 -3.7977346 -1.4591942

F -3.8912990 0.8389038 5.2856183

F -0.8592292 2.5304147 0.4276625

F -2.4382158 -1.3307464 4.4666630

F -0.5809395 -0.7626983 -2.6250659

F -4.7183930 2.6967902 3.4679214

F -0.9947417 5.1047274 -3.5129623

F -2.4752129 3.1706369 -4.7438409

F -1.8181355 -1.6292712 1.8489748

F -4.1142247 2.4091066 0.8561691

F -0.3865791 -3.2031439 -3.7970675

F -0.1948234 4.7776153 -0.9192230

F -3.1551977 0.9280370 -3.4159367

F -4.0768559 0.2984284 -0.9384313

F -2.0209149 -5.2351569 -2.9908796

F -4.1755591 -2.3488522 0.0427052

F -3.9096990 -4.7978039 -1.0690633

C 5.4392211 -2.7016190 -0.4804339

C 4.7071619 -2.6500415 0.8712509

C 6.2624333 -0.1562474 1.7218489

C 3.0651916 -2.3164243 3.8542958

C 6.6419890 0.6357880 2.9894106

C 3.9297411 -1.1076787 3.4560730

C 2.1602804 -1.9127403 -1.1408814

C 1.7109371 -1.5592127 0.1398340

C 1.2851209 0.2740574 1.9115278

C 1.9761826 -3.2022282 -1.6249744

C 1.0230826 -2.5064845 0.9035535

C 1.3089054 -4.1504099 -0.8440946

C 0.8197983 -3.7960678 0.4127392

H 5.5481378 -3.7368721 -0.8180358

H 4.8890744 -2.1596159 -1.2537858

H 6.4413212 -2.2657442 -0.4125361

H 5.2817371 -3.2282448 1.6139559

H 3.7340164 -3.1457281 0.8042433

H 6.9500683 -1.0096465 1.6209283

H 6.4510639 0.4477415 0.8302897

H 3.5472259 -3.2566085 3.5710017

H 2.0812313 -2.3034202 3.3803006

H 2.9109193 -2.3307557 4.9374941

H 6.6984533 -0.0214649 3.8614070

H 7.6240541 1.1019730 2.8635255

H 5.9226348 1.4260839 3.2209728

H 4.8667733 -1.1629659 4.0298087

H 3.4689412 -0.1646596 3.7740271

H 2.6676566 -1.1761510 -1.7572214

H 0.2032077 0.2785371 1.7513108

H 1.5072260 -0.3889189 2.7465023

H 1.5896682 1.2892817 2.1716839

H 2.3426215 -3.4677235 -2.6107246

H 0.6290716 -2.2428024 1.8767424

H 1.1619800 -5.1578922 -1.2210282

H 0.2854893 -4.5230639 1.0158836

H 1.6671336 0.5308226 -0.1708414

Si 4.0685446 1.5210855 -0.2637622

C 4.8096405 2.7687486 0.9153974

C 3.9082884 3.1426402 2.1081643

H 4.9788946 3.6609670 0.2949006

H 5.7990739 2.4656013 1.2664461

H 4.3640669 3.9402357 2.7022591

H 2.9273232 3.4997982 1.7765171

H 3.7460982 2.2880166 2.7736771

C 5.2105180 0.8343651 -1.5763650

C 5.8366736 1.9715157 -2.4164903

H 4.6270207 0.1717889 -2.2292416

H 6.0023860 0.2133947 -1.1478180

H 6.4603507 1.5562310 -3.2134447

H 5.0706562 2.5976357 -2.8858628

H 6.4671773 2.6194330 -1.7994545

C 2.6105499 2.3709605 -1.1002009

C 1.9964700 1.7359159 -2.3615745

H 3.0685032 3.3326698 -1.3810727

H 1.8355163 2.6435682 -0.3732612

H 1.3404202 2.4466980 -2.8723905

H 2.7697202 1.4374036 -3.0751534

H 1.3985103 0.8474766 -2.1366571

TSAB.xyz charge = +1

75

Energy = -3538.854890899

P -1.7003630 -0.0647050 0.8598156

H -0.2348218 0.0176200 -0.1454910

Si 1.1287644 0.0613300 -1.1411014

O 3.1786312 0.3171748 -2.8418754

C 4.3139576 0.0550610 -3.2574822

C 1.2222764 2.6503466 -2.4759846

C -0.3224858 -2.4929146 1.0876574

C 0.5529836 -3.3621702 3.1480512

C 0.0867060 -2.2335498 3.8218978

C -4.0276138 -1.0165244 -2.9951454

C -0.7900616 -1.3450982 1.7336520

C -3.2591632 0.1446390 -2.9256394

C 0.3435248 -3.4973890 1.7759190

C 1.3795222 1.9288200 -1.1236324

C -4.0664508 -1.8983340 -1.9150350

C -2.5283226 0.4078438 -1.7752660

C -2.5525956 -0.4527738 -0.6726776

C -3.3419752 -1.6073700 -0.7663326

C -0.5868216 -1.2443334 3.1164422

C -0.2139378 2.1396668 1.7928050

C 0.4254668 -0.7359286 -2.6938154

C 2.8379594 -0.6790026 1.1914164

C 1.0653244 -2.0784218 -3.0978392

C -1.4037622 1.6696140 1.2292254

C -0.0383150 3.4753650 2.1302658

C 2.3303446 -1.0484864 -0.2098388

C -1.0716914 4.3807956 1.8975700

C -2.4315036 2.6017406 1.0186004

C -2.2718018 3.9437318 1.3372362

C 5.3386120 0.7614936 -1.0993444

C 5.4928290 0.1673860 -2.3628186

C 4.5074704 -0.3943478 -4.6836914

C 6.4172774 0.8614896 -0.2289268

C 6.7548742 -0.3188748 -2.7428244

C 7.6674686 0.3629338 -0.6108426

C 7.8343586 -0.2258478 -1.8669490

F -4.7241594 -1.2856322 -4.0961416

F -0.5255068 -2.6485606 -0.2317128

F -3.2155402 0.9857354 -3.9625558

F 0.7981516 1.2913382 2.0241768

F -4.8033034 -3.0096814 -1.9879668

F 1.1949414 -4.3161826 3.8173808

F 0.2861968 -2.1117718 5.1366072

F -1.7807670 1.5232982 -1.7393880

F -3.3991920 -2.4682976 0.2593228

F 1.1126364 3.8908418 2.6664816

F 0.7802426 -4.5843374 1.1329964

F -1.0248334 -0.1679950 3.7846898

F -3.0191704 -0.1805358 1.7931060

F -0.9144534 5.6637958 2.2116808

F -3.5971230 2.2122378 0.4829198

F -3.2607132 4.8138282 1.1165874

H 1.4056582 3.7222120 -2.3469166

H 0.6762336 2.3695766 -0.4091568

H 1.9308930 2.2632708 -3.2101622

H 0.2129518 2.5307066 -2.8794974

H -0.6516716 -0.8876526 -2.5667896

H 2.0568658 -0.7835146 1.9473300

H 0.9179274 -2.8437634 -2.3309816

H 2.3786886 2.1142778 -0.7106376

H 3.2042992 0.3503228 1.2358854

H 0.6099806 -2.4430336 -4.0244368

H 1.9206870 -2.0648698 -0.2112578

H 0.5411826 -0.0044550 -3.5017810

H 3.6639270 -1.3395882 1.4731162

H 2.1385128 -1.9690418 -3.2671012

H 3.1819132 -1.0969334 -0.9006704

H 4.3667986 1.1544244 -0.8228786

H 3.5587800 -0.3229588 -5.2162190

H 6.2905734 1.3273242 0.7437756

H 5.2681320 0.2118678 -5.1862180

H 4.8561682 -1.4340542 -4.7022364

H 6.8938142 -0.7804456 -3.7149380

H 8.5112472 0.4370988 0.0691260

H 8.8053990 -0.6113446 -2.1626898

TSAC.xyz charge = +1

98

Energy = -4066.876318737

P -3.8945147 0.6802136 -0.1060934

H -2.3318874 0.3281089 -0.0247640

Si -0.4154231 -0.0752541 0.0109788

C -1.1600803 -2.7876053 -0.9274646

C -2.6209087 3.1603835 0.2942950

C -2.8631117 5.0678624 -1.1437539

C -3.6955297 4.3228136 -1.9792030

C -4.2594945 -0.5488206 4.3374298

C -3.4543492 2.3873236 -0.5177478

C -3.7972022 -1.4726104 3.4007188

C -2.3230003 4.4849511 0.0019084

C -0.3890143 -1.4893839 -1.2144166

C -4.6199282 0.7359138 3.9310585

C -3.6864307 -1.0922617 2.0695752

C -4.0238849 0.1896924 1.6335017

C -4.5139570 1.0879312 2.5897902

C -3.9880274 3.0017362 -1.6588538

C -3.2108020 -0.4233890 -2.5846202

C -0.3983745 -0.5659017 1.8206675

C 0.8578647 1.5298841 -2.0141263

C -0.6395287 0.4506129 2.9478160

C -4.0071506 -0.5345714 -1.4427810

C -3.2841514 -1.3377516 -3.6263880

C 0.0225990 1.5917236 -0.7200050

C -4.1772418 -2.4055475 -3.5333227

C -4.9145392 -1.5989094 -1.3869835

C -4.9955983 -2.5369034 -2.4113882

C 4.1385301 1.7464063 -0.6910131

C 3.2367661 2.0039602 0.3446427

C 3.5207654 0.5738619 2.4063854

C 4.6740992 2.7917375 -1.4427984

C 2.8844821 3.3300609 0.6194052

C 4.3160059 4.1120511 -1.1635480

C 3.4196393 4.3798118 -0.1275124

F -4.3665134 -0.8968613 5.6172510

F -2.0776073 2.6198252 1.4002843

F -3.4649618 -2.7098016 3.7814201

F -2.3511430 0.6092260 -2.7029101

F -5.0715386 1.6169628 4.8268760

F -2.5839457 6.3346318 -1.4387114

F -4.2123849 4.8812604 -3.0759018

F -3.2545508 -2.0090499 1.1823100

F -4.8715397 2.3303995 2.2332943

F -2.5059969 -1.2022475 -4.7049446

F -1.5172953 5.1906851 0.8020445

F -4.7813310 2.3137177 -2.4915706

F -5.5040892 1.0109508 -0.1820098

F -4.2514371 -3.2954435 -4.5197638

F -5.7099409 -1.7568312 -0.3203809

F -5.8527031 -3.5567725 -2.3272142

H -2.2388744 -2.6318124 -0.9730446

H -0.6498813 -1.0885347 -2.1997976

H -0.8973759 -3.5478195 -1.6686593

H -0.9280812 -3.1942868 0.0604740

H -1.0850385 -1.4144430 1.9154463

H 1.0852445 2.5463765 -2.3478074

H -1.6744870 0.7937009 2.9666006

H 0.6835061 -1.7151432 -1.2960186

H 0.3137156 1.0248987 -2.8165927

H -0.4203179 -0.0142343 3.9132434

H -0.9216941 2.0993112 -0.9445588

H 0.6016673 -1.0074540 1.9236130

H 1.8027808 1.0127403 -1.8494579

H -0.0032708 1.3341289 2.8524370

H 0.5229763 2.2065032 0.0347401

H 4.4125004 0.7240563 -0.9315202

H 3.1067407 -0.2677126 2.9703725

H 5.3673322 2.5744884 -2.2502668

H 4.5462766 0.3468290 2.1128998

H 3.5437658 1.4496870 3.0619691

H 2.1833951 3.5437671 1.4243593

H 4.7288266 4.9257041 -1.7524774

H 3.1322865 5.4033047 0.0951582

O 2.2924297 -0.2672586 0.4021081

Si 3.1784751 -1.6605194 -0.0222509

C 2.6453760 0.8997494 1.1975691

H 1.6866191 1.2629112 1.5821190

C 4.9626621 -1.6957774 0.5848449

C 5.7064251 -2.9147821 -0.0062976

H 4.9896149 -1.7526984 1.6785358

H 5.4944194 -0.7768561 0.3092703

H 6.7341060 -2.9584472 0.3687973

H 5.2152476 -3.8558969 0.2645875

H 5.7543563 -2.8656151 -1.0990617

C 2.2691976 -3.1259232 0.7384631

C 2.4131199 -3.2543979 2.2668325

H 2.6480559 -4.0393850 0.2601661

H 1.2064345 -3.0843357 0.4705820

H 1.8393150 -4.1055205 2.6482627

H 3.4584128 -3.4007695 2.5563987

H 2.0554350 -2.3581432 2.7872925

C 3.1727704 -1.7365433 -1.9157268

C 2.9128578 -3.1291346 -2.5252522

H 4.1476689 -1.3659469 -2.2631375

H 2.4405913 -1.0208649 -2.3087985

H 1.9264147 -3.5131615 -2.2418424

H 2.9545549 -3.0929330 -3.6188722

H 3.6538045 -3.8605878 -2.1871644

TSBC.xyz charge = +1

62

Energy = -1439.225218548

H 0.0960261 -1.9553934 -0.9952622

Si -0.0494382 1.7006292 0.0262757

O 0.4499663 -0.0641480 -0.2563489

C -0.2462823 -0.9516608 -1.2996050

C 0.0647283 2.4262733 2.8999247

C -0.7819276 1.8207448 1.7643332

C 1.5240667 2.6935595 -0.2450174

C -2.7649136 2.4011034 -0.8601842

C 2.1909187 2.4951225 -1.6192990

C -1.2968606 2.2384697 -1.2949828

C -2.3056870 -1.0930426 0.1558393

C -1.7469560 -0.9034092 -1.1238251

C 0.3184810 -0.6377793 -2.6734712

C -3.6940338 -1.1336595 0.3315515

C -2.6094062 -0.7702986 -2.2281607

C -4.5456566 -1.0008329 -0.7753665

C -3.9991904 -0.8212342 -2.0535764

H -0.5634712 2.6145896 3.7867250

H 0.8788063 1.7545920 3.2191221

H 0.5189505 3.3880424 2.6058418

H -1.6834200 2.4469189 1.6195299

H -1.1807060 0.8330367 2.0581396

H 1.1860793 3.7459875 -0.1417870

H 2.2521886 2.5466113 0.5692830

H -2.8725943 3.1808328 -0.0865069

H -3.1815785 1.4643400 -0.4582176

H -3.3864875 2.7057120 -1.7186326

H 1.4889490 2.6971106 -2.4471908

H 3.0527775 3.1718586 -1.7438969

H 2.5592037 1.4617250 -1.7435912

H -0.9012586 3.2202899 -1.6272235

H -1.2383829 1.5947633 -2.1867145

H -1.6502096 -1.2137926 1.0212604

H 1.4168150 -0.6774407 -2.6523515

H -0.0343391 -1.3971895 -3.3903205

H 0.0106997 0.3533384 -3.0382107

H -4.1106902 -1.2783864 1.3330769

H -2.2063600 -0.6324648 -3.2351481

H -5.6311068 -1.0387869 -0.6420410

H -4.6563738 -0.7186474 -2.9224462

Si 1.7273084 -1.0417255 0.6426353

C 2.7738157 0.1275453 1.6809306

C 4.1051924 0.6199541 1.0787170

H 2.9867029 -0.4673780 2.5928149

H 2.1678336 0.9746701 2.0459647

H 4.6230790 1.2894565 1.7858203

H 4.7851532 -0.2216095 0.8653858

H 3.9627135 1.1747261 0.1371270

C 2.8253353 -1.9325498 -0.6057903

C 2.3549971 -3.2389096 -1.2730406

H 3.7061188 -2.1630988 0.0311245

H 3.2126462 -1.2138476 -1.3530926

H 3.1999337 -3.7440488 -1.7701938

H 1.9362330 -3.9448179 -0.5352476

H 1.5871083 -3.0652268 -2.0455378

C 0.7960397 -2.2713222 1.7245028

C 0.1789079 -1.7420719 3.0328954

H 1.5681009 -3.0318992 1.9650266

H 0.0406982 -2.8204297 1.1302950

H -0.2490795 -2.5670249 3.6262498

H 0.9301390 -1.2351399 3.6622528

H -0.6316915 -1.0169157 2.8451679

TSC1.xyz charge = +1

98

Energy = -4066.917115829

P -2.3235112 0.3064821 -0.2195340

H -0.9201302 -0.0747396 0.1766387

Si 5.0149895 -1.0121611 1.1166275

O 4.0252575 0.1283644 0.3840851

C 0.8335016 -0.7088907 0.7062826

C -0.8738067 2.7003789 -0.3580119

C -0.7817627 4.1733935 -2.2490929

C -1.5731969 3.2809834 -2.9722438

C -3.4325717 0.6249878 4.2709819

C -1.6829477 1.7938587 -1.0460750

C -2.8995249 -0.5601178 3.7661137

C -0.4347863 3.8869959 -0.9297240

C -3.6363298 1.7138684 3.4235203

C -2.5674155 -0.6307046 2.4199060

C -2.7612525 0.4363070 1.5428691

C -3.3120777 1.6081182 2.0750612

C -2.0229805 2.1125942 -2.3663120

C -1.4881034 -1.5686481 -2.1167620

C -2.4112915 -1.2761975 -1.1111144

C -1.5038306 -2.7744535 -2.8055066

C -2.4486182 -3.7401133 -2.4618006

C -3.3687763 -2.2491995 -0.8099728

C -3.3847590 -3.4781513 -1.4615495

F -3.7487286 0.7166913 5.5613200

F -0.5205228 2.4494126 0.9216971

F -2.7107852 -1.6130404 4.5692638

F -0.5710419 -0.6425945 -2.4659477

F -4.1448599 2.8495690 3.9107125

F -0.3486079 5.2954874 -2.8216230

F -1.8929353 3.5528910 -4.2412033

F -2.0633514 -1.7923364 1.9513900

F -3.5197180 2.6780285 1.2924982

F -0.6263700 -3.0129534 -3.7873683

F 0.3187799 4.7426775 -0.2311330

F -2.7750437 1.2760854 -3.0957048

F -3.8808324 0.6808948 -0.6573107

F -2.4632307 -4.9115052 -3.0984524

F -4.2895515 -2.0240755 0.1397425

F -4.2948565 -4.4039877 -1.1428427

C 5.3083519 -2.3808630 -1.4122355

C 4.9502386 -2.5764905 0.0720227

C 6.7961861 -0.3827199 1.2300548

C 3.4389283 -2.5836587 3.0203639

C 7.1773206 0.3736796 2.5185213

C 4.3641173 -1.3638300 2.8591509

C 1.4721364 -2.2579300 -1.0595926

C 0.8706697 -2.0312761 0.2112116

C 0.7206760 -0.3216639 2.1248953

C 1.6137855 -3.5407288 -1.5525173

C 0.4088190 -3.1491470 0.9617155

C 1.1246114 -4.6226219 -0.8085088

C 0.5240295 -4.4247778 0.4453007

H 5.2641151 -3.3263278 -1.9646777

H 4.6180537 -1.6802020 -1.8938418

H 6.3189060 -1.9746807 -1.5302141

H 5.6338055 -3.3069285 0.5289699

H 3.9492598 -3.0194158 0.1554675

H 7.4517668 -1.2592542 1.1237688

H 7.0121052 0.2452794 0.3560607

H 3.9676294 -3.5106834 2.7769700

H 2.5708465 -2.5316215 2.3565923

H 3.0660372 -2.6711703 4.0468047

H 7.1321208 -0.2860964 3.3907582

H 8.1968737 0.7700194 2.4562128

H 6.5063053 1.2164549 2.7132483

H 5.2372642 -1.5008966 3.5109635

H 3.8702419 -0.4564632 3.2362011

H 1.8590924 -1.4115188 -1.6143967

H 0.1700326 0.6125307 2.2530417

H 0.3256335 -1.0990475 2.7768002

H 1.7523774 -0.1006816 2.4469253

H 2.0972682 -3.7099593 -2.5075089

H -0.0448249 -3.0010464 1.9328658

H 1.2202458 -5.6299997 -1.2007788

H 0.1629966 -5.2759717 1.0109753

H 1.2034809 0.0599200 0.0321169

Si 4.2525568 1.5989629 -0.3770429

C 4.8792319 2.8641653 0.8665332

C 4.0259172 2.9546055 2.1468225

H 4.9024664 3.8433961 0.3679168

H 5.9215769 2.6385278 1.1257934

H 4.4202877 3.7037187 2.8419004

H 2.9905062 3.2316065 1.9167769

H 3.9999391 1.9942675 2.6740559

C 5.4182034 1.4340038 -1.8465874

C 5.6621297 2.7696598 -2.5797562

H 4.9982103 0.6980426 -2.5455569

H 6.3778649 1.0168803 -1.5166549

H 6.3122524 2.6310024 -3.4503436

H 4.7241386 3.2107981 -2.9359240

H 6.1399168 3.5025638 -1.9210165

C 2.5749394 2.1981157 -1.0096509

C 2.0590455 1.5464301 -2.3031952

H 2.6734176 3.2814610 -1.1683785

H 1.8397630 2.0992556 -0.1990334

H 1.0867826 1.9479144 -2.6080626

H 2.7540536 1.7111613 -3.1314178

H 1.9396128 0.4636800 -2.2015415

65

6. Comparing Activity of Catalyst 1, 5, 6, 7 & 8

A subset of ketones where selected from the substrate scope and hydrodeoxygenation

was catalytically preformed with catalyst 6, 7, and 8 to compare their reactivity with

catalyst 1 and 5. General procedure provided in section 3.2 was followed and yields

determined using 1H NMR.

Substrate Catalyst Silane Temp

(°C)

Tim

e

%

Conversion

Product

12a

[FP(C6F5)3]+ (1) 2.1 eq

Et3SiH

25 5 89

12c

[(SIMes)FPPh2]2+ (5) 5 84

[(SIMes)FPEt2]2+ (6) 5 96

[(SIMes)FPMe2]2+ (7) 5 67

[(SIMes)ClPPh2]2+ (8) 2 >99

13a

[FP(C6F5)3]+ (1) 2.1 eq

Et3SiH

25 5 >99

13c

[(SIMes)FPPh2]2+ (5) 5 >99

[(SIMes)FPEt2]2+ (6) 5 >99

[(SIMes)FPMe2]2+ (7) 5 >99

[(SIMes)ClPPh2]2+ (8) 1 >99

14a

[FP(C6F5)3]+ (1) 2.1 eq

Et3SiH

25 5 >99

14c

[(SIMes)FPPh2]2+ (5) 5 >99

[(SIMes)FPEt2]2+ (6) 5 >99

[(SIMes)FPMe2]2+ (7) 5 >99

[(SIMes)ClPPh2]2+ (8) 1 >99

15a

[FP(C6F5)3]+ (1) 2.1 eq

Et3SiH

25 5 88

15c

[(SIMes)FPPh2]2+ (5) 25 5 >99

[(SIMes)FPEt2]2+ (6) 25 5 92

[(SIMes)FPMe2]2+ (7) 25 5 >99

[(SIMes)ClPPh2]2+ (8) 50 72 56

66

7. References

[1] C. B. Caputo, L. J. Houjet, R. Dobrovetsky, D. W. Stephan, Science 2013, 341, 1374.

16a

[FP(C6F5)3]+ (1) 2.1 eq

Et3SiH

25 12 71

16c

[(SIMes)FPPh2]2+ (5) 5 >99

[(SIMes)FPEt2]2+ (6) 12 >99

[(SIMes)FPMe2]2+ (7) 12 61

[(SIMes)ClPPh2]2+ (8) 2 >99

17a

[FP(C6F5)3]+ (1) 2 eq

Et3SiH

25 2 >99

17c

[(SIMes)FPPh2]2+ (5) 3 >99

[(SIMes)FPEt2]2+ (6) 2 >99

[(SIMes)FPMe2]2+ (7) 2 >99

18a

[FP(C6F5)3]+ (1) 7 eq

Et3SiH

25 5 >99

18c

[(SIMes)FPPh2]2+ (5) 5 >99

[(SIMes)FPEt2]2+ (6) 5 >99

[(SIMes)FPMe2]2+ (7) 5 >99

19a

[FP(C6F5)3]+ (1) 2.1 eq

Et3SiH

25 2 >99

19c

[(SIMes)FPPh2]2+ (5) 12 >99

[(SIMes)FPEt2]2+ (6) 12 >99

[(SIMes)FPMe2]2+ (7) 4 >99

[(SIMes)ClPPh2]2+ (8) 4 >99

26a

[FP(C6F5)3]+ (1) 3 eq

Et3SiH

25

72 >99

Olefin poylmerization

[FP(C6F5)3]+ (1) 3 eq

Et3SiH

50 24 >99

[(SIMes)FPPh2]2+ (5) 24 >99

[(SIMes)FPEt2]2+ (6) 24 >99

[(SIMes)FPMe2]2+ (7) 24 >99

67

.[2] L. J. Hounjet, C. B. Caputo, D. W. Stephan, Dalton Trans. 2013, 42, 2629.

[3] (a) T. W. Hudnall, Y. M. Kim, M. W. P. Bebbington, D. Bourissou and F. P. Gabba¨ı,

J. Am. (b) C. W. Chiu, Y. Kim and F. P. Gabba¨ı, J. Am. Chem. Soc., 2009, 131, 60

[4] J. B. Lambert, S. Zhang, S. M. Ciro, Organometallics 1994, 2430.

[5] A. J. Arduengo, R. Krafczyk, R. Schmutzler, H. A. Craig, J. R. Goerlich, W. J.

Marshall,

M. Unverzagt, Tetrahedron 1999, 55, 14523.

[6] M. Holthausen, M. Mehta, D. W. Stephan, Angew. Chem. Int. Ed. 2014, 53, 6538.

[7] a) SAINT 7.23A, Bruker AXS, Inc: Madison, Wisconsin, 2006; b) G. M. Sheldrick,

SADABS, Bruker AXS, Inc.: Madison, Wisconsin, 2004.

[8] G. M. Sheldrick, SHELXL-97, Program for crystal structure determination, University

of Göttingen, Germany, 1997.

[9] A. S. S. Sido, S. Walspurger, J. Barbiche, J. Sommer, Chem. Eur. J. 2010, 16, 3215.

[10] J. E. M. N. Klein, S. Rommel, B. Plietker, B. Organometallics 2014, 20, 5802-5810.

[11] D. Srimani, A. Bej, A. Sarkar, Journal of Organic Chemistry 2010, 75, 4296.

[12] J. M. Gacoyne, P. J. Mitchell, L. Phillips, J. Chem. Soc. Perkins Trans. 1977, 8, 1051.

[13] N. Sakai, K. Kawana, R. Ikeda, Y. Nakaike, T. Konakahara, Eur. J. Org. Chem. 2011,

17, 3178.

[14] Y. Nakai, F. Yamada, Organic Magnetic Resonance 1978, 11, 607.

[15] L.-G. Xie, Z.-X. Wang, Chem. Eur. J. 2011, 17, 4972.

[16] L. Zetta, G. Gatti, Journal of Magnetic Resonance 1972, 4, 585.

[17] T. Otsubo, F. Ogura, H. Yamaguchi, H. Higuchi, S. Misumi, Synthetic Commun. 1980,

10, 595.

[18] J. W. De Haan, L. J. M. van de Ven, Organic Magnetic Resonance 1973, 5, 147.

[19] S. Dıez-Gonzalez, H. Kaur, F. K. Zinn, E. D. Stevens, S. P. Nolan, J. Org. Chem,

2005, 12, 4784-4796.

[20] G. A. Molander, B. Canturk, Organic Letters 2010, 10, 2135.

[21] H. A. Kalviri, C. F. Petten, F. M. Kerton, Chem. Commun. 2009, 34, 5171.

[22] T. Maegawa, A. Akashi, K. Yaguchi, Y. Iwasaki, M. Shigetsura, Y. Monguchi, H.

Sajiki, Chem. Eur. J. 2009, 15, 6953-6963.

[23] T. Cohen; J. P. Sherbine; J. R. Matz; R. R. Hutchins; B. M. McHenry; P. R. Willey, J.

Am. Chem. Soc. 1984, 106, 3245-3252.

68

[24] a) R. Ahlrichs, M. Bär, M. Häser, H. Horn and C. Kölmel, Chem. Phys. Lett. 1989,

162, 165-169; b) R. Ahlrichs, M. K. Armbruster, R. A. Bachorz, M. Bär, H.-P. Baron,

R. Bauernschmitt, F. A. Bischoff, S. Böcker, N. Crawford, P. Deglmann, F. D. Sala,

M. Diedenhofen, M. Ehrig, K. Eichkorn, S. Elliott, F. Furche, A. Glöß, F. Haase, M.

Häser, C. Hättig, A. Hellweg, S. Höfener, H. Horn, C. Huber, U. Huniar, M.

Kattannek, W. Klopper, A. Köhn, C. Kölmel, M. Kollwitz, K. May, P. Nava, C.

Ochsenfeld, H. Öhm, M. Pabst, H. Patzelt, D. Rappoport, O. Rubner, A. Schäfer, U.

Schneider, M. Sierka, D. P. Tew, O. Treutler, B. Unterreiner, M. v. Arnim, F.

Weigend, P. Weis, H. Weiss and N. Winter in TURBOMOLE version 6.4

TURBOMOLE GmbH, 2012.

[25] J. Tao, J. P. Perdew, V. N. Staroverov and G. E. Scuseria, Phys. Rev. Lett. 2003, 91,

146401.

[26] a) S. Grimme, S. Ehrlich and H. Krieg, J. Chem. Phys. 2010, 132, 154104-154119; b)

S. Grimme, S. Ehrlich and L. Goerigk, J. Comput. Chem. 2011, 32, 1456-1465.

[27] a) A. Schaefer, C. Huber and R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835; b) F.

Weigend, M. Häser, H. Patzelt and R. Ahlrichs, Chem. Phys. Lett. 1998, 143, 294; c)

F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297-3305.

[28] A. Klamt and G. Schüürmann, J. Chem. Soc., Perkin Trans. 1993, 2, 799.

[29] a) K. Eichkorn, F. Weigend, O. Treutler and R. Ahlrichs, Theor. Chem. Acc. 1997, 97,

119; b) P. Deglmann, K. May, F. Furche and R. Ahlrichs, Chem. Phys. Lett. 2004,

384, 103.

[30] S. Grimme, Chem. Eur. J. 2012, 18, 9955.

[31] a) F. Eckert and A. Klamt, in COSMOtherm, Version C3.0, Release 14.01,

COSMOlogic GmbH & Co. KG, Leverkusen, Germany, 2013; b) Eckert, F. and A.

Klamt, AIChE Journal, 2002, 48, 369.

[32] Y. Zhao and D. G. Truhlar, J. Phys. Chem. A 2005, 109, 5656.

[33] S. Grimme, J. Chem. Phys. 2006, 124, 034108-034116.

[34] F. Weigend, F. Furche and R. Ahlrichs, J. Chem. Phys. 2003, 119, 12753.

i In order to obtain pure 1,2-bis(4-methoxyphenyl)ethane , it was necessary to leave the reaction mixture under reduced pressure for an extended amount of time. Despite the high molecular weight of the product, these conditions caused significant loss of yield. However the NMR spectra of the reaction mixture shows quantitative conversion to the single 1,2-bis(4-methoxyphenyl)ethane product.