Upload
hamien
View
220
Download
0
Embed Size (px)
Citation preview
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
1
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
2
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
3
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
4
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,
5
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-
6
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
7
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)
8
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.