Voltammetric Characterisation of Diferrocenylborinic Acid in … · 2019-05-31 · X-Ray notes: Supp. Figure S17: Crystal structure and X-Ray data of diferrocenylborinic acid (1)

Supporting Information

Voltammetric Characterisation of DiferrocenylborinicAcid in Organic Solution and in Aqueous Media when

Immobilised into a Titanate Nanosheet Film

Martin Konhefr,∗1,2,3 Adam C. Sedgwick,1 Tony D. James,1 Karel Lacina,3

Petr Skládal,2,3 Budi Riza Putra,1,4 Christian Harito,5 Dmitry V. Bavykin,5

Frank C. Walsh,5 Paul R. Raithby,1 Gabriele Kociok-Köhn,1,6

and Frank Marken1

*[email protected]

1 Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK2 Department of Biochemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno,Czech Republic

3 Central European Institute of Technology, Masaryk University, Kamenice 5, 625 00 Brno, Czech Republic4 Department of Chemistry, Faculty of Mathematics and Natural Sciences, Bogor Agricultural University,Bogor, West Java, Indonesia

5 Energy Technology Research Group, Faculty of Engineering and the Environment,

University of Southampton, SO17 1BJ, Southampton, UK6 Material and Chemical Characterisation Facility (MC2), University of Bath, Bath BA2 7AY, UK

1

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019

List of Figures

S1 1H NMR spectrum of 1 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 4S2 11B NMR spectrum of 1 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 4S3 13C NMR spectrum of 1 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 5S4 1H NMR spectrum of 2 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 5S5 11B NMR spectrum of 2 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 6S6 13C NMR spectrum of 2 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 6S7 1H NMR spectrum of 3 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 7S8 11B NMR spectrum of 3 (chloroform-d1) . . . . . . . . . . . . . . . . . . . . . . . . 7S9 HRMS of diferrocenylborinic acid (1) in acetonitrile . . . . . . . . . . . . . . . . . 9S10 HRMS of trisferrocenylborane (2) in acetonitrile . . . . . . . . . . . . . . . . . . . 10S11 FTIR of diferrocenylborinic acid (1, red prism) . . . . . . . . . . . . . . . . . . . . 12S12 FTIR of diferrocenylborinic acid (1, ochre powder) . . . . . . . . . . . . . . . . . 13S13 FTIR of trisferrocenylborane (2, red powder) . . . . . . . . . . . . . . . . . . . . . 14S14 CV of 1 in dichloromethane, scan rates 0.0125 – 1.0 Vs−1 . . . . . . . . . . . . . 16S15 SEC of diferrocenylborinic acid (1) in acetonitrile . . . . . . . . . . . . . . . . . . 18S16 SEC of diferrocenylborinic acid (1) in dichloromethane . . . . . . . . . . . . . . . 19S17 Crystal structure and X-Ray data of diferrocenylborinic acid (1) . . . . . . . . . 20

2

NMR notes:

AbbreviationsFcH = ferrocene,(FcBO)3 = ferroceneboronic acid anhydride (boroxine),imp = impurities

Structures of 1 and 2

3

Supp. Figure S1: 1H NMR spectrum of 1 (chloroform-d1)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0Chemical shift (ppm)

Fc2BOH (CDCl3)

10.0

0

8.00

1.00

4.15

4.52

4.54

4.92

7.26

*imp

Supp. Figure S2: 11B NMR spectrum of 1 (chloroform-d1)

1015202530354045505560657075808590Chemical shift (ppm)

Fc2BOH (CDCl3)

46.0

5

8

4

Supp. Figure S3: 13C NMR spectrum of 1 (chloroform-d1)


Fc2BOH (CDCl3)

68.7

372

.41

73.6

676

.65

77.0

877

.50



Fc3B (CDCl3)

15.0

0

6.00

6.00

4.17

4.22

4.62

4.89

7.26

7.37

*FcH

benzene*

5


-30-25-20-15-10-5051015202530354045505560657075808590Chemical shift (ppm)

Fc3B (CDCl3)

62.7

3

Supp. Figure S6: 13C NMR spectrum of 2 (chloroform-d1)


Fc3B (CDCl3)

69.0

0

72.4

3

76.6

577

.07

77.1

577

.49

*FcH

6



FcBnprop, reaction mixture with (FcBO)3 (CDCl3)

2.96

3.10

2.06

2.08

1.93

2.00

5.01

4.03

0.92

0.94

0.97

1.00

1.02

1.56

1.58

1.61

1.63

1.66

1.68

1.70

1.73

3.60

3.62

3.96

3.98

3.99

4.01

4.13

4.34

4.37

4.42

7.26

(FcBO)3*

(FcBO)3 *

imp*



FcBnprop, reaction mixture with (FcBO)3 (CDCl3)

30.3

3

7

MS notes:

General – 1 and 2 in acetonitrile, other conditions as in Supp. Figures S9–S10

8

Supp. Figure S9: HRMS of diferrocenylborinic acid (1) in acetonitrile

Fc2BOHC20H19Fe2BO exact mass: 398.0232

expected mass: [M]+ = 398.0227 observed mass: [M]+ = 398.0229 mass accuracy = 0.5 ppm

ESI + (MMI) nitrogen flow 5 L/min, gas temperature 325°C, nebulizer 45 psig, skimmer 65 V, Vcap 1500 V, fragmentor 30 V, dissolved in acetonitrile

Fc2BOHC20H19Fe2BO exact mass: 398.0232

expected mass: [M]+ = 398.0227 observed mass: [M]+ = 398.0229 mass accuracy = 0.5 ppm


9

Supp. Figure S10: HRMS of trisferrocenylborane (2) in acetonitrile

Fc3BC30H27Fe3B exact mass: 566.0261

expected mass: [M]+ = 566.0256 observed mass: [M]+ = 566.0248 mass accuracy = - 1.4 ppm


*

* - system impurity – 2xACN+Cu – 144.9822

[C20H18Fe2]+ = 370.0102







[C30H26Fe3]+ = 554.0079

[C30H27Fe3BO]+ = 582.0205

10

FTIR notes:

Table 1: FTIR comparison of Fc2BOH (1) and Fc3B (2):

Fc2BOH(red prism)

Fc2BOH(ochre powder)

Fc3B(this study)

Intensity(this study)

Fc3B (in KBr)([1])

Assignment([1])

3593 (BOH) 3596 (BOH) Medium -3110 CH stretching

3092 3091 3089 Weak -3080 CH stretching

2923 Weak -1774 1771 Weak -

1690 Weak -1651 1650 Weak 1653 CC deformation

1610 CC stretching1449 1452 1427 Strong -1407 1407 Medium -1375 1375 1375 Strong 1375 Ring breathing

1352 Weak 1350 CH deformation (∥)1277 1277 1250 Strong -

1187 Weak 1189 CH deformation (⊥)1147 1149 Weak -1101 1102 1105 Strong 1106 CH deformation (⊥)1042 1043 1052 Strong 1053 CC deformation (∥)995 998 999 Strong 1000 CH deformation (∥)923 925 Medium -816 817 814 Strong 818 CH deformation (⊥)751 752 759 Strong -

697 Medium -688 688 Strong -

590 -569 569 Medium 576 CCC deformation (⊥)536 536 Medium -475 476 485 Strong 489 Ring tilt463 464 468 Strong 470 Fe-ring stretching

11

Supp. Figure S11: FTIR of diferrocenylborinic acid (1, red prism)

3915.76

3593.14

3401.73

3091.72

2925.18

1774.191693.541650.701574.971449.361406.801390.201374.881349.921337.151323.221302.531276.761192.811179.541146.671101.421081.001066.141042.001013.29994.90923.31897.53871.06815.98762.81750.72700.91687.57645.60597.12568.73550.60535.95507.14475.49463.22

5001000

15002000

25003000

3500

Wavenum

ber cm-1

70 75 80 85 90

Transmittance [%]

12

Supp. Figure S12: FTIR of diferrocenylborinic acid (1, ochre powder)

3595.93

3091.23

2960.492924.852849.90

1771.391649.871452.111407.381390.201375.271350.051336.361323.121302.641276.971192.121180.321148.641101.721081.981067.851042.991014.80998.14924.99897.69870.80816.81763.34751.73701.01688.38645.95596.17568.61536.25476.49463.97

5001000

15002000

25003000

3500

Wavenum

ber cm-1

50 60 70 80 90

Transmittance [%]

13

Supp. Figure S13: FTIR of trisferrocenylborane (2, red powder)

3597.70

3089.05

2956.752923.23

1770.111689.531647.271452.861427.321409.191391.291375.161351.961324.211299.861250.161187.151104.641077.281051.64999.12941.33926.58893.30872.06814.38771.26759.18697.37629.01591.92571.55550.62538.35485.47468.03

5001000

15002000

25003000

3500

Wavenum

ber cm-1

40 50 60 70 80 90 100

Transmittance [%]

14

Electrochemistry notes:

General – 1 mM solution of 1 with 50 mM TBAH; scan rates as indicated in each Figure

Figure S14: In dichloromethane (using glassy carbon electrode), as described in the maintext of this article, the same step-by-step oxidation of both ferrocenyl moieties is also observedfrom the scan rate approximately 0.4 Vs−1 and higher. During lower scan rates in DCM, newredox pairs emerge when scanning from first to third scan. This can be contributed to anintermediate form. Such intermediate is dependent on the oxidation state of 1 which is formedafter the first step-by-step double oxidation of Fc2BOH during first forward scan. The verycomplementary results are spectroelectrochemical experiments (see Supp. Figs. S15–S16).

15

Supp. Figure S14: CV of 1 in dichloromethane, scan rates 0.0125 – 1.0 Vs−1

16

Spectroelectrochemistry notes:

General – 1 mM solution of 1 with 50 mM TBAH; scan rate 10 mVs−1, step 5 mV

17

Supp. Figure S15: SEC of diferrocenylborinic acid (1) in acetonitrile

18

Supp. Figure S16: SEC of diferrocenylborinic acid (1) in dichloromethane

19

X-Ray notes:

Supp. Figure S17: Crystal structure and X-Ray data of diferrocenylborinic acid (1)

C1

C5

C4

C3

C2

C8

C9

C7

C6

C10

B1

O1

H1a

C20

C16

C17

C18

Fe1

C19

C11

C15

C12

C14C13

The cif file of the structure has been deposited in the Cambridge Structural Database,deposition number CCDC1894130.

20

Table 1. Crystal data and structure refinement for e18fm1a.

Identification code e18fm1a

Empirical formula C20 H19 B Fe2 O

Formula weight 397.86

Temperature 150.01(10) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21/c

Unit cell dimensions a = 7.5541(2) Å = 90°.

b = 10.4332(3) Å = 105.628(3)°.

c = 10.6451(3) Å = 90°.

Volume 807.96(4) Å3

Z 2

Density (calculated) 1.635 Mg/m3

Absorption coefficient 1.797 mm-1

F(000) 408

Crystal size 0.284 x 0.192 x 0.126 mm3

Theta range for data collection 3.414 to 27.511°.

Index ranges -9<=h<=9, -13<=k<=13, -13<=l<=13

Reflections collected 21598

Independent reflections 1850 [R(int) = 0.0313]

Completeness to theta = 25.242° 99.7 %

Absorption correction Analytical

Max. and min. transmission 0.834 and 0.678

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 1850 / 1 / 185

Goodness-of-fit on F2 1.091

Final R indices [I>2sigma(I)] R1 = 0.0236, wR2 = 0.0541

R indices (all data) R1 = 0.0273, wR2 = 0.0556

Extinction coefficient n/a

Largest diff. peak and hole 0.310 and -0.223 e.Å-3

21

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)

for e18fm1a. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

Fe(1) 7453(4) 4410(3) 7387(2) 18(1)

Fe(2) 2633(4) 5787(2) 2384(2) 17(1)

O(1) 2763(3) 3420(2) 5065(2) 39(1)

B(1) 4044(4) 4306(3) 4924(3) 24(1)

C(1) 1817(11) 7510(8) 2153(6) 23(1)

C(2) 1860(12) 7272(9) 3475(6) 28(1)

C(3) 604(14) 6264(10) 3497(8) 29(1)

C(4) -214(14) 5880(9) 2189(9) 30(2)

C(5) 535(14) 6650(9) 1359(6) 33(2)

C(6) 3366(5) 3901(3) 2394(3) 29(1)

C(7) 3748(5) 4536(4) 1317(2) 24(1)

C(8) 4992(3) 5553(3) 1808(3) 27(1)

C(9) 5378(3) 5546(3) 3190(3) 24(1)

C(10) 4373(4) 4525(3) 3552(2) 21(1)

C(11) 10159(13) 4157(9) 7953(9) 26(2)

C(12) 9252(13) 3654(10) 6707(7) 32(2)

C(13) 8117(12) 2624(8) 6890(6) 22(1)

C(14) 8324(11) 2491(8) 8249(6) 26(1)

C(15) 9586(12) 3438(9) 8907(6) 23(1)

C(16) 6363(4) 6032(2) 6419(2) 23(1)

C(17) 6970(5) 6272(4) 7781(3) 26(1)

C(18) 6004(6) 5432(4) 8412(2) 35(1)

C(19) 4801(3) 4673(2) 7441(3) 23(1)

C(20) 5022(3) 5044(3) 6209(2) 20(1)

________________________________________________________________________________

22

Table 3. Bond lengths [Å] for e18fm1a.

_____________________________________________________

Fe(1)-C(12) 1.877(11)

Fe(1)-C(11) 1.987(10)

Fe(1)-C(20) 2.035(4)

Fe(1)-C(16) 2.037(3)

Fe(1)-C(13) 2.037(9)

Fe(1)-C(19) 2.039(4)

Fe(1)-C(17) 2.041(5)

Fe(1)-C(18) 2.042(5)

Fe(1)-C(15) 2.199(9)

Fe(1)-C(14) 2.227(9)

Fe(2)-C(5) 1.892(11)

Fe(2)-C(1) 1.895(10)

Fe(2)-C(10) 2.032(4)

Fe(2)-C(9) 2.035(4)

Fe(2)-C(6) 2.044(5)

Fe(2)-C(8) 2.049(4)

Fe(2)-C(7) 2.054(5)

Fe(2)-C(4) 2.106(11)

Fe(2)-C(2) 2.110(10)

Fe(2)-C(3) 2.231(10)

O(1)-B(1) 1.375(4)

O(1)-H(1A) 0.827(19)

B(1)-C(10) 1.563(4)

B(1)-C(20) 1.571(4)

C(1)-C(2) 1.4200

C(1)-C(5) 1.4200

C(1)-H(1) 0.9500

C(2)-C(3) 1.4200

C(2)-H(2) 0.9500

C(3)-C(4) 1.4200

C(3)-H(3) 0.9500

C(4)-C(5) 1.4200

C(4)-H(4) 0.9500

23

C(5)-H(5) 0.9500

C(6)-C(10) 1.4200

C(6)-C(7) 1.4200

C(6)-H(6) 0.9500

C(7)-C(8) 1.4200

C(7)-H(7) 0.9500

C(8)-C(9) 1.4200

C(8)-H(8) 0.9500

C(9)-C(10) 1.4200

C(9)-H(9) 0.9500

C(11)-C(15) 1.4200

C(11)-C(12) 1.4200

C(11)-H(11) 0.9500

C(12)-C(13) 1.4200

C(12)-H(12) 0.9500

C(13)-C(14) 1.4200

C(13)-H(13) 0.9500

C(14)-C(15) 1.4200

C(14)-H(14) 0.9500

C(15)-H(15) 0.9500

C(16)-C(17) 1.4200

C(16)-C(20) 1.4200

C(16)-H(16) 0.9500

C(17)-C(18) 1.4200

C(17)-H(17) 0.9500

C(18)-C(19) 1.4200

C(18)-H(18) 0.9500

C(19)-C(20) 1.4200

C(19)-H(19) 0.9500

_____________________________________________________

24

Table 4. Bond angles [°] for e18fm1a.

_____________________________________________________

C(12)-Fe(1)-C(11) 43.0(2)

C(12)-Fe(1)-C(20) 121.7(3)

C(11)-Fe(1)-C(20) 156.1(3)

C(12)-Fe(1)-C(16) 113.0(2)

C(11)-Fe(1)-C(16) 120.5(3)

C(20)-Fe(1)-C(16) 40.82(6)

C(12)-Fe(1)-C(13) 42.3(2)

C(11)-Fe(1)-C(13) 69.6(3)

C(20)-Fe(1)-C(13) 112.5(3)

C(16)-Fe(1)-C(13) 136.3(2)

C(12)-Fe(1)-C(19) 152.5(3)

C(11)-Fe(1)-C(19) 161.4(3)

C(20)-Fe(1)-C(19) 40.80(7)

C(16)-Fe(1)-C(19) 68.64(11)

C(13)-Fe(1)-C(19) 116.3(3)

C(12)-Fe(1)-C(17) 131.9(3)

C(11)-Fe(1)-C(17) 106.9(3)

C(20)-Fe(1)-C(17) 68.62(11)

C(16)-Fe(1)-C(17) 40.76(8)

C(13)-Fe(1)-C(17) 174.0(2)

C(19)-Fe(1)-C(17) 68.55(14)

C(12)-Fe(1)-C(18) 166.8(3)

C(11)-Fe(1)-C(18) 124.2(3)

C(20)-Fe(1)-C(18) 68.59(12)

C(16)-Fe(1)-C(18) 68.57(14)

C(13)-Fe(1)-C(18) 145.2(2)

C(19)-Fe(1)-C(18) 40.72(8)

C(17)-Fe(1)-C(18) 40.70(10)

C(12)-Fe(1)-C(15) 68.1(3)

C(11)-Fe(1)-C(15) 39.25(17)

C(20)-Fe(1)-C(15) 164.5(3)

C(16)-Fe(1)-C(15) 150.7(3)

C(13)-Fe(1)-C(15) 65.6(2)

25

C(19)-Fe(1)-C(15) 124.9(3)

C(17)-Fe(1)-C(15) 115.1(3)

C(18)-Fe(1)-C(15) 103.8(3)

C(12)-Fe(1)-C(14) 67.5(2)

C(11)-Fe(1)-C(14) 65.8(2)

C(20)-Fe(1)-C(14) 131.6(2)

C(16)-Fe(1)-C(14) 171.9(2)

C(13)-Fe(1)-C(14) 38.58(15)

C(19)-Fe(1)-C(14) 107.0(2)

C(17)-Fe(1)-C(14) 145.1(2)

C(18)-Fe(1)-C(14) 113.0(2)

C(15)-Fe(1)-C(14) 37.41(14)

C(5)-Fe(2)-C(1) 44.1(2)

C(5)-Fe(2)-C(10) 164.7(3)

C(1)-Fe(2)-C(10) 145.9(3)

C(5)-Fe(2)-C(9) 154.4(3)

C(1)-Fe(2)-C(9) 115.5(3)

C(10)-Fe(2)-C(9) 40.87(7)

C(5)-Fe(2)-C(6) 130.2(3)

C(1)-Fe(2)-C(6) 173.0(3)

C(10)-Fe(2)-C(6) 40.78(8)

C(9)-Fe(2)-C(6) 68.57(11)

C(5)-Fe(2)-C(8) 123.0(3)

C(1)-Fe(2)-C(8) 110.7(2)

C(10)-Fe(2)-C(8) 68.53(11)

C(9)-Fe(2)-C(8) 40.69(7)

C(6)-Fe(2)-C(8) 68.30(13)

C(5)-Fe(2)-C(7) 112.8(3)

C(1)-Fe(2)-C(7) 134.3(2)

C(10)-Fe(2)-C(7) 68.43(13)

C(9)-Fe(2)-C(7) 68.36(11)

C(6)-Fe(2)-C(7) 40.55(10)

C(8)-Fe(2)-C(7) 40.49(8)

C(5)-Fe(2)-C(4) 41.2(2)

C(1)-Fe(2)-C(4) 69.9(3)

26

C(10)-Fe(2)-C(4) 124.4(3)

C(9)-Fe(2)-C(4) 160.9(3)

C(6)-Fe(2)-C(4) 108.2(3)

C(8)-Fe(2)-C(4) 157.4(3)

C(7)-Fe(2)-C(4) 122.3(3)

C(5)-Fe(2)-C(2) 69.8(3)

C(1)-Fe(2)-C(2) 41.10(18)

C(10)-Fe(2)-C(2) 111.6(3)

C(9)-Fe(2)-C(2) 105.1(3)

C(6)-Fe(2)-C(2) 145.0(2)

C(8)-Fe(2)-C(2) 130.1(3)

C(7)-Fe(2)-C(2) 170.4(3)

C(4)-Fe(2)-C(2) 66.0(2)

C(5)-Fe(2)-C(3) 67.2(3)

C(1)-Fe(2)-C(3) 67.1(2)

C(10)-Fe(2)-C(3) 104.1(3)

C(9)-Fe(2)-C(3) 124.9(3)

C(6)-Fe(2)-C(3) 115.9(3)

C(8)-Fe(2)-C(3) 164.3(3)

C(7)-Fe(2)-C(3) 151.4(3)

C(4)-Fe(2)-C(3) 38.09(17)

C(2)-Fe(2)-C(3) 38.06(16)

B(1)-O(1)-H(1A) 113(3)

O(1)-B(1)-C(10) 119.6(3)

O(1)-B(1)-C(20) 114.5(3)

C(10)-B(1)-C(20) 125.9(2)

C(2)-C(1)-C(5) 108.0

C(2)-C(1)-Fe(2) 77.6(4)

C(5)-C(1)-Fe(2) 67.9(4)

C(2)-C(1)-H(1) 126.0

C(5)-C(1)-H(1) 126.0

Fe(2)-C(1)-H(1) 120.2

C(1)-C(2)-C(3) 108.0

C(1)-C(2)-Fe(2) 61.3(3)

C(3)-C(2)-Fe(2) 75.6(4)

27

C(1)-C(2)-H(2) 126.0

C(3)-C(2)-H(2) 126.0

Fe(2)-C(2)-H(2) 128.4

C(4)-C(3)-C(2) 108.0

C(4)-C(3)-Fe(2) 66.2(4)

C(2)-C(3)-Fe(2) 66.4(3)

C(4)-C(3)-H(3) 126.0

C(2)-C(3)-H(3) 126.0

Fe(2)-C(3)-H(3) 133.2

C(3)-C(4)-C(5) 108.0

C(3)-C(4)-Fe(2) 75.7(4)

C(5)-C(4)-Fe(2) 61.3(3)

C(3)-C(4)-H(4) 126.0

C(5)-C(4)-H(4) 126.0

Fe(2)-C(4)-H(4) 128.2

C(1)-C(5)-C(4) 108.0

C(1)-C(5)-Fe(2) 68.1(4)

C(4)-C(5)-Fe(2) 77.5(4)

C(1)-C(5)-H(5) 126.0

C(4)-C(5)-H(5) 126.0

Fe(2)-C(5)-H(5) 120.1

C(10)-C(6)-C(7) 108.0

C(10)-C(6)-Fe(2) 69.15(14)

C(7)-C(6)-Fe(2) 70.14(11)

C(10)-C(6)-H(6) 126.0

C(7)-C(6)-H(6) 126.0

Fe(2)-C(6)-H(6) 126.3

C(8)-C(7)-C(6) 108.0

C(8)-C(7)-Fe(2) 69.56(13)

C(6)-C(7)-Fe(2) 69.31(11)

C(8)-C(7)-H(7) 126.0

C(6)-C(7)-H(7) 126.0

Fe(2)-C(7)-H(7) 126.7

C(7)-C(8)-C(9) 108.0

C(7)-C(8)-Fe(2) 69.95(17)

28

C(9)-C(8)-Fe(2) 69.12(13)

C(7)-C(8)-H(8) 126.0

C(9)-C(8)-H(8) 126.0

Fe(2)-C(8)-H(8) 126.5

C(10)-C(9)-C(8) 108.0

C(10)-C(9)-Fe(2) 69.43(12)

C(8)-C(9)-Fe(2) 70.19(13)

C(10)-C(9)-H(9) 126.0

C(8)-C(9)-H(9) 126.0

Fe(2)-C(9)-H(9) 126.0

C(9)-C(10)-C(6) 108.0

C(9)-C(10)-B(1) 126.5(2)

C(6)-C(10)-B(1) 124.1(2)

C(9)-C(10)-Fe(2) 69.70(12)

C(6)-C(10)-Fe(2) 70.06(17)

B(1)-C(10)-Fe(2) 115.3(2)

C(15)-C(11)-C(12) 108.0

C(15)-C(11)-Fe(1) 78.5(3)

C(12)-C(11)-Fe(1) 64.4(4)

C(15)-C(11)-H(11) 126.0

C(12)-C(11)-H(11) 126.0

Fe(1)-C(11)-H(11) 122.6

C(13)-C(12)-C(11) 108.0

C(13)-C(12)-Fe(1) 74.9(4)

C(11)-C(12)-Fe(1) 72.6(4)

C(13)-C(12)-H(12) 126.0

C(11)-C(12)-H(12) 126.0

Fe(1)-C(12)-H(12) 118.4

C(12)-C(13)-C(14) 108.0

C(12)-C(13)-Fe(1) 62.8(4)

C(14)-C(13)-Fe(1) 78.0(3)

C(12)-C(13)-H(13) 126.0

C(14)-C(13)-H(13) 126.0

Fe(1)-C(13)-H(13) 124.4

C(15)-C(14)-C(13) 108.0

29

C(15)-C(14)-Fe(1) 70.2(3)

C(13)-C(14)-Fe(1) 63.4(3)

C(15)-C(14)-H(14) 126.0

C(13)-C(14)-H(14) 126.0

Fe(1)-C(14)-H(14) 131.9

C(11)-C(15)-C(14) 108.0

C(11)-C(15)-Fe(1) 62.3(3)

C(14)-C(15)-Fe(1) 72.4(3)

C(11)-C(15)-H(15) 126.0

C(14)-C(15)-H(15) 126.0

Fe(1)-C(15)-H(15) 130.8

C(17)-C(16)-C(20) 108.0

C(17)-C(16)-Fe(1) 69.79(18)

C(20)-C(16)-Fe(1) 69.53(14)

C(17)-C(16)-H(16) 126.0

C(20)-C(16)-H(16) 126.0

Fe(1)-C(16)-H(16) 126.2

C(16)-C(17)-C(18) 108.0

C(16)-C(17)-Fe(1) 69.45(14)

C(18)-C(17)-Fe(1) 69.70(11)

C(16)-C(17)-H(17) 126.0

C(18)-C(17)-H(17) 126.0

Fe(1)-C(17)-H(17) 126.4

C(17)-C(18)-C(19) 108.0

C(17)-C(18)-Fe(1) 69.60(11)

C(19)-C(18)-Fe(1) 69.50(15)

C(17)-C(18)-H(18) 126.0

C(19)-C(18)-H(18) 126.0

Fe(1)-C(18)-H(18) 126.5

C(20)-C(19)-C(18) 108.0

C(20)-C(19)-Fe(1) 69.46(12)

C(18)-C(19)-Fe(1) 69.78(18)

C(20)-C(19)-H(19) 126.0

C(18)-C(19)-H(19) 126.0

Fe(1)-C(19)-H(19) 126.3

30

C(19)-C(20)-C(16) 108.0

C(19)-C(20)-B(1) 121.7(2)

C(16)-C(20)-B(1) 129.9(2)

C(19)-C(20)-Fe(1) 69.74(12)

C(16)-C(20)-Fe(1) 69.64(13)

B(1)-C(20)-Fe(1) 120.8(2)

_____________________________________________________________

31

Table 5. Anisotropic displacement parameters (Å2x 103) for e18fm1a. The anisotropic

displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________

Fe(1) 14(1) 16(1) 22(1) 0(1) 4(1) 1(1)

Fe(2) 14(1) 16(1) 21(1) 0(1) 4(1) 2(1)

O(1) 41(1) 39(1) 30(1) 7(1) -3(1) -21(1)

B(1) 21(1) 19(2) 28(2) 6(1) -3(1) -2(1)

C(1) 24(2) 22(2) 26(4) -1(3) 10(3) -4(2)

C(2) 39(2) 32(2) 20(3) -3(3) 18(3) 10(2)

C(3) 33(3) 28(3) 35(3) -1(2) 24(2) 2(2)

C(4) 21(4) 21(4) 53(5) 10(3) 18(3) -2(3)

C(5) 30(3) 40(4) 21(3) 5(2) -4(2) 6(2)

C(6) 25(2) 20(2) 38(3) -8(2) 2(2) 8(2)

C(7) 19(2) 29(3) 24(2) -13(2) 6(1) -2(2)

C(8) 18(1) 34(2) 31(2) -5(2) 11(1) 0(1)

C(9) 16(1) 35(2) 21(2) -1(2) 6(1) 4(1)

C(10) 14(2) 15(2) 30(2) -1(1) 1(1) -2(1)

C(11) 9(3) 31(4) 36(3) -3(3) 4(3) 6(3)

C(12) 40(3) 37(3) 31(3) 12(2) 30(2) 18(3)

C(13) 27(2) 23(2) 18(3) -9(2) 11(2) 2(2)

C(14) 37(2) 27(2) 17(3) 0(2) 9(3) -1(2)

C(15) 18(2) 23(2) 24(2) 2(2) 2(2) -2(2)

C(16) 25(2) 14(2) 26(2) 3(1) 0(1) 1(1)

C(17) 31(2) 24(2) 19(2) -6(2) 0(1) 6(2)

C(18) 32(2) 43(3) 30(2) -8(2) 7(2) 11(2)

C(19) 16(1) 32(2) 22(2) 7(2) 10(2) 6(1)

C(20) 17(2) 15(2) 25(2) 5(1) 2(1) 3(1)

______________________________________________________________________________

32

Table 6. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)

for e18fm1a.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(1) 2522 8135 1854 28

H(2) 2598 7709 4214 34

H(3) 356 5910 4253 35

H(4) -1106 5223 1918 36

H(5) 233 6599 434 39

H(6) 2575 3184 2349 34

H(7) 3258 4319 424 29

H(8) 5480 6135 1302 32

H(9) 6170 6123 3770 29

H(11) 11002 4853 8120 31

H(12) 9380 3954 5893 38

H(13) 7354 2114 6220 26

H(14) 7723 1876 8649 32

H(15) 9978 3568 9823 27

H(16) 6780 6458 5763 28

H(17) 7864 6887 8196 31

H(18) 6140 5386 9325 42

H(19) 3989 4030 7589 27

H(1A) 2150(50) 3130(40) 4360(20) 45(11)

________________________________________________________________________________

33

Table 7. Torsion angles [°] for e18fm1a.

________________________________________________________________

C(5)-Fe(2)-C(1)-C(2) 115.5(2)

C(10)-Fe(2)-C(1)-C(2) -46.0(5)

C(9)-Fe(2)-C(1)-C(2) -83.8(3)

C(8)-Fe(2)-C(1)-C(2) -127.9(3)

C(7)-Fe(2)-C(1)-C(2) -167.8(4)

C(4)-Fe(2)-C(1)-C(2) 76.2(2)

C(3)-Fe(2)-C(1)-C(2) 35.29(14)

C(10)-Fe(2)-C(1)-C(5) -161.5(5)

C(9)-Fe(2)-C(1)-C(5) 160.7(4)

C(8)-Fe(2)-C(1)-C(5) 116.6(3)

C(7)-Fe(2)-C(1)-C(5) 76.7(4)

C(4)-Fe(2)-C(1)-C(5) -39.27(16)

C(2)-Fe(2)-C(1)-C(5) -115.5(2)

C(3)-Fe(2)-C(1)-C(5) -80.2(2)

C(5)-C(1)-C(2)-C(3) 0.0

Fe(2)-C(1)-C(2)-C(3) -61.5(4)

C(5)-C(1)-C(2)-Fe(2) 61.5(4)

C(1)-C(2)-C(3)-C(4) 0.0

Fe(2)-C(2)-C(3)-C(4) -52.8(3)

C(1)-C(2)-C(3)-Fe(2) 52.8(3)

C(2)-C(3)-C(4)-C(5) 0.0

Fe(2)-C(3)-C(4)-C(5) -52.8(3)

C(2)-C(3)-C(4)-Fe(2) 52.8(3)

C(2)-C(1)-C(5)-C(4) 0.0

Fe(2)-C(1)-C(5)-C(4) 68.0(4)

C(2)-C(1)-C(5)-Fe(2) -68.0(4)

C(3)-C(4)-C(5)-C(1) 0.0

Fe(2)-C(4)-C(5)-C(1) -61.7(4)

C(3)-C(4)-C(5)-Fe(2) 61.7(4)

C(10)-Fe(2)-C(5)-C(1) 137.6(12)

C(9)-Fe(2)-C(5)-C(1) -43.7(7)

C(6)-Fe(2)-C(5)-C(1) -174.6(3)

C(8)-Fe(2)-C(5)-C(1) -86.2(3)

34

C(7)-Fe(2)-C(5)-C(1) -130.9(3)

C(4)-Fe(2)-C(5)-C(1) 115.48(19)

C(2)-Fe(2)-C(5)-C(1) 39.20(15)

C(3)-Fe(2)-C(5)-C(1) 80.1(2)

C(1)-Fe(2)-C(5)-C(4) -115.48(19)

C(10)-Fe(2)-C(5)-C(4) 22.1(11)

C(9)-Fe(2)-C(5)-C(4) -159.2(8)

C(6)-Fe(2)-C(5)-C(4) 69.9(3)

C(8)-Fe(2)-C(5)-C(4) 158.3(4)

C(7)-Fe(2)-C(5)-C(4) 113.6(3)

C(2)-Fe(2)-C(5)-C(4) -76.3(2)

C(3)-Fe(2)-C(5)-C(4) -35.34(14)

C(10)-C(6)-C(7)-C(8) 0.0

Fe(2)-C(6)-C(7)-C(8) 58.99(14)

C(10)-C(6)-C(7)-Fe(2) -58.99(14)

C(6)-C(7)-C(8)-C(9) 0.0

Fe(2)-C(7)-C(8)-C(9) 58.84(11)

C(6)-C(7)-C(8)-Fe(2) -58.84(11)

C(7)-C(8)-C(9)-C(10) 0.0

Fe(2)-C(8)-C(9)-C(10) 59.35(16)

C(7)-C(8)-C(9)-Fe(2) -59.35(16)

C(8)-C(9)-C(10)-C(6) 0.0

Fe(2)-C(9)-C(10)-C(6) 59.83(17)

C(8)-C(9)-C(10)-B(1) -166.8(3)

Fe(2)-C(9)-C(10)-B(1) -107.0(3)

C(8)-C(9)-C(10)-Fe(2) -59.83(17)

C(7)-C(6)-C(10)-C(9) 0.0

Fe(2)-C(6)-C(10)-C(9) -59.61(11)

C(7)-C(6)-C(10)-B(1) 167.2(3)

Fe(2)-C(6)-C(10)-B(1) 107.6(2)

C(7)-C(6)-C(10)-Fe(2) 59.61(11)

O(1)-B(1)-C(10)-C(9) 167.7(2)

C(20)-B(1)-C(10)-C(9) -10.5(4)

O(1)-B(1)-C(10)-C(6) 2.9(4)

C(20)-B(1)-C(10)-C(6) -175.3(2)

35

O(1)-B(1)-C(10)-Fe(2) 85.1(3)

C(20)-B(1)-C(10)-Fe(2) -93.1(3)

C(15)-C(11)-C(12)-C(13) 0.0

Fe(1)-C(11)-C(12)-C(13) -67.1(4)

C(15)-C(11)-C(12)-Fe(1) 67.1(4)

C(11)-Fe(1)-C(12)-C(13) 114.83(16)

C(20)-Fe(1)-C(12)-C(13) -89.3(3)

C(16)-Fe(1)-C(12)-C(13) -134.5(3)

C(19)-Fe(1)-C(12)-C(13) -47.0(5)

C(17)-Fe(1)-C(12)-C(13) -178.1(3)

C(18)-Fe(1)-C(12)-C(13) 131.4(11)

C(15)-Fe(1)-C(12)-C(13) 77.26(18)

C(14)-Fe(1)-C(12)-C(13) 36.72(13)

C(20)-Fe(1)-C(12)-C(11) 155.9(3)

C(16)-Fe(1)-C(12)-C(11) 110.6(3)

C(13)-Fe(1)-C(12)-C(11) -114.83(16)

C(19)-Fe(1)-C(12)-C(11) -161.8(6)

C(17)-Fe(1)-C(12)-C(11) 67.1(3)

C(18)-Fe(1)-C(12)-C(11) 16.6(11)

C(15)-Fe(1)-C(12)-C(11) -37.57(13)

C(14)-Fe(1)-C(12)-C(11) -78.11(19)

C(11)-C(12)-C(13)-C(14) 0.0

Fe(1)-C(12)-C(13)-C(14) -65.6(4)

C(11)-C(12)-C(13)-Fe(1) 65.6(4)

C(12)-C(13)-C(14)-C(15) 0.0

Fe(1)-C(13)-C(14)-C(15) -55.9(4)

C(12)-C(13)-C(14)-Fe(1) 55.9(4)

C(12)-C(11)-C(15)-C(14) 0.0

Fe(1)-C(11)-C(15)-C(14) 57.9(3)

C(12)-C(11)-C(15)-Fe(1) -57.9(3)

C(13)-C(14)-C(15)-C(11) 0.0

Fe(1)-C(14)-C(15)-C(11) -51.9(3)

C(13)-C(14)-C(15)-Fe(1) 51.9(3)

C(20)-C(16)-C(17)-C(18) 0.0

Fe(1)-C(16)-C(17)-C(18) -59.24(12)

36

C(20)-C(16)-C(17)-Fe(1) 59.24(12)

C(16)-C(17)-C(18)-C(19) 0.0

Fe(1)-C(17)-C(18)-C(19) -59.09(14)

C(16)-C(17)-C(18)-Fe(1) 59.09(14)

C(17)-C(18)-C(19)-C(20) 0.0

Fe(1)-C(18)-C(19)-C(20) -59.15(10)

C(17)-C(18)-C(19)-Fe(1) 59.15(10)

C(18)-C(19)-C(20)-C(16) 0.0

Fe(1)-C(19)-C(20)-C(16) -59.35(17)

C(18)-C(19)-C(20)-B(1) 173.8(3)

Fe(1)-C(19)-C(20)-B(1) 114.4(3)

C(18)-C(19)-C(20)-Fe(1) 59.35(17)

C(17)-C(16)-C(20)-C(19) 0.0

Fe(1)-C(16)-C(20)-C(19) 59.40(17)

C(17)-C(16)-C(20)-B(1) -173.1(4)

Fe(1)-C(16)-C(20)-B(1) -113.7(3)

C(17)-C(16)-C(20)-Fe(1) -59.40(17)

O(1)-B(1)-C(20)-C(19) 9.5(4)

C(10)-B(1)-C(20)-C(19) -172.2(2)

O(1)-B(1)-C(20)-C(16) -178.2(3)

C(10)-B(1)-C(20)-C(16) 0.0(5)

O(1)-B(1)-C(20)-Fe(1) 93.4(3)

C(10)-B(1)-C(20)-Fe(1) -88.3(3)

________________________________________________________________

37

References

[1] T. López and A. Campero, “Trisferrocenylborane and its amine adducts,” Journal ofOrganometallic Chemistry, vol. 378, no. 1, pp. 91–98, nov 1989. [Online]. Available:https://dx.doi.org/10.1016/0022-328X(89)85009-0

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https://dx.doi.org/10.1016/0022-328X(89)85009-0

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