supplementary information - nature · 2013-07-23 · 1-methyl-4-prop-1-ynylbenzene-d. 3 (26a) 55...

NATURE CHEMISTRY | www.nature.com/naturechemistry 1

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1693

1

A frustrated Lewis pair approach to catalytic reduction of alkynes to

cis-alkenes

Konstantin Chernichenko, Ádám Madarász, Imre Pápai, Martin Nieger, Markku Leskelä and Timo Repo

Table of Contents:

General experimental 2

Alkynes 3 Section S1. (Hept-3-ynyloxy)(trimethyl)silane (19a) 3 Section S2. (Hept-6-en-3-ynyloxy)(trimethyl)silane (25a) 4 Section S3. Hept-2-ynylbenzene (14a) 5 Section S4. Tert-butyl(dimethyl)silyl octadec-9-ynoate (16a) 6

Catalytic hydrogenations 8 Section S5. General protocol for hydrogenation in standard conditions 8 Section S6. Scale-up experiments 8 Section S7. Catalytic activity determination 8 Section S8. Attempted high-pressure hydrogenation of alkenes 11b and 12b 9 Section S9. Determination of maximum value of turnover number 10

Alkenes 11 Section S10. (2Z)-but-2-ene (10b) 11 Section S11. (2Z)-hept-2-enylbenzene (14b) 11 Section S12. (1Z)-but-1-enylbenzene (15b) 12 Section S13. [(1Z)-5-chloropent-1-enyl](triethyl)silane (18b) 13 Section S14. 1-[(1Z)-hex-1-enyl]cyclohexene (17b) 14 Section S15. [(3Z)-hept-3-enyloxy](trimethyl)silane (19b) 15 Section S16. Tert-butyl(dimethyl)silyl (9Z)-octadec-9-enoate (16b) 16 Section S17. (3Z,9Z)-dodeca-3,9-diene (20b) 17 Section S18. Dodeca-5,7-diene (24b-d) 18 Section S19. (3Z)-2-methylhexa-1,3-diene (23b) 21 Section S20. (3E)-2-methylhexa-1,3-diene (23c)10 21 Section S21. (Z)-stilbene (21b) 25

Mechanistic studies 27 Section S22. N,N-dimethyl-2-[(pentafluorophenyl)boryl]aniline (8) 27 Section S23. 2-[[(Z)-1,2-Diphenylvinyl](pentafluorophenyl)boryl]-N,N-dimethylaniline (27c) 29 Section S24. Hydroboration of enyne 23a 33 Section S25. N,N-dimethyl-2-[[(3Z)-2-methylhex-3-enyl](pentafluorophenyl)boryl]aniline (S4) 33 Section S26. 2-[Hexyl(pentafluorophenyl)boryl]-N,N-dimethylaniline (30a) 36 Section S27. 2-[[(1Z)-1-ethylbut-1-enyl](pentafluorophenyl)boryl]-N,N-dimethylaniline (27b) 39 Section S28. 2-[(1-Ethylbutyl)(pentafluorophenyl)boryl]-N,N-dimethylaniline (30c) 42 Section S29. [2-(Dimethylammonio)phenyl](hex-1-ynyl)bis(pentafluorophenyl)borate(1-) (31) 46 Section S30. Reaction of 6 with hex-1-yne under hydrogen 49 Section S31. Competitive hydroboration experiments 51 Section S32. Hydroboration reversibility 53 Section S33. Reversibility of cis-hex-3-ene (11b) hydroboration. 54

Isotope-labelling experiments: 55 Section S34. 1-Methyl-4-prop-1-ynylbenzene-d3 (26a) 55 Section S35. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d3 (26b) 56 Section S36. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d5 (26c) 58 Section S37. Hydrogenation of 1-methyl-4-prop-1-ynylbenzene-d3 with HD. 60

1

A frustrated-Lewis-pair approach to catalytic reduction of alkynes to

cis-alkenes


Table of Contents:







1

A frustrated-Lewis-pair approach to catalytic reduction of alkynes to

cis-alkenes


Table of Contents:






Isotope-labelling experiments: 55 Section S34. 1-Methyl-4-prop-1-ynylbenzene-d3 (26a) 55 Section S35. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d3 (26b) 56 Section S36. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d5 (26c) 58 Section S37. Hydrogenation of 1-methyl-4-prop-1-ynylbenzene-d3 with HD. 60 1


cis-alkenes


Table of Contents:







1


cis-alkenes


Table of Contents:







© 2013 Macmillan Publishers Limited. All rights reserved.



2

Section S38. Stoichiometric reaction of the catalyst 8 with the model substrate 26a and subsequent treatment with D2. 61 Section S39. Experiment A: 62 Section S40. N,N-dimethyl-2-[[(Z)-1-methyl-2-(4-methylphenyl)vinyl](pentafluorophenyl)boryl]aniline-d3 (27d) 62 Section S41. N,N-dimethyl-2-[[(1Z)-1-(4-methylphenyl)prop-1-enyl](pentafluorophenyl)boryl]aniline-d3 (27e) 63 Section S42. Experiment B: 68 Section S43. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d4 (26e) 68 Section S44. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d4 (26d) 68 Section S45. [(Z)-2-phenylvinyl]benzene-d1 (21c) 70 Section S46. 2-[(1-ethylbutyl)(pentafluorophenyl)boryl]-N,N-dimethylaniline-d2 75 Section S47. Details of attempted catalytic hydrogenation with (C6F5)2BH and (C6F5)3B 79

Computational Protocol 81

Computational Results 82 Section S48. Generation of the catalyst 82 Section S49. Catalytic cycle for the hydrogenation of but-2-yne 85 Section S50. Catalytic cycle for the hydrogenation of cis-but-2-ene 90 Section S51. Catalytic cycle for the hydrogenation of ethylene 92 Section S52. Total energy data of the calculated structures 93 Section S53. Cartesian coordinates of the calculated structures 94

General experimental

All the solvents were dried by conventional methods and stored over molecular

sieves. Deutereited solvents were purchased from Eurisotop or Merck and dried by standing over molecular sieves (3 Å) and used without additional purification. All operations were performed under argon atmosphere by a conventional Schlenk technique or in a glove box (Mbraun Unilab). Reagents were purchased from Sigma-Aldrich and dried by conventional methods if needed. Organometallics were purchased from Acros Organics (n-butyllithium, boron trichloride solution), Strem (dimethyltin dichloride) and used as received.

Hydrogen (5.0) was purchased from AGA and dried additionally by passing through the cylinder with molecular sieves. Hydrogenations (at 2 bar) were performed in thick-wall 25 ml Schlenk vessels or in J. Young valve NMR tubes purchased from Wilmad. Schlenk vessels were equiped with gas-tight teflon valves and Glindemann PTFE sealing rings.

NMR spectra were recorded at Varian Mercury 300 (1H, 13C, 19F) or Varian Inova 500 (1H, 13C, 10B, 11B) spectrometers. If not otherwise stated:

• NMR spectra were recorded at 27 °C; • 13C spectra were 1H decoupled; • signals in 13C spectra are singlets; • 10B, 11B spectra were not 1H decoupled; baseline corrected.

Chemical shifts for the 1H and 13C spectra were referenced to the residual 1H/13C resonances of the deuterated solvent:

• C6D6: δ = 7.16; δ = 128.00; • CDCl3: δ = 7.25; δ = 77.0; • CD2Cl2: δ = 5.32; δ = 53.84;




3

• C6D5Br: δ = 7.29; δ = 121.19 (s);1 and are reported as parts per million relative to tetramethylsilane.

Chemical shifts for the 11B, 10B and 19F spectra were referenced to external standard (BF3·Et2O, CFCl3).

HRMS spectra were recorded at Bruker micrOTOF using ESI method for the ionic aminoborane adducts or APCI method for the covalent compounds in acetonitrile and toluene as a solvent, respectively. The solutions of sodium formate and the Tunemix mixture were used as standards for ESI and APCI, respectively.

2-[Bis(pentafluorophenyl)boryl]-N,N-dimethylaniline 6 was prepared as reported.2

Alkynes

All alkynes were dried by standing over 3Å molecular sieves prior to use. 1-

Ethynyl-4-methylbenzene, 3,9-dodecadiyne 20a, 2-methyl-1-hexen-3-yne 23a, 6-hepten-3-yn-1-ol, 3-heptyn-1-ol, 1-phenyl-1-propyne, 1-phenyl-1-butyne 15a, 2-hexyne 13a, hex-1-ene 12b, hex-1-yne 12a, cis-hex-3-ene 11b, but-2-yne 10a were purchased from Sigma-Aldrich and used as received. (5-Chloropentyl)(triethyl)silane 16a was purchased from Sigma-Aldrich as “1-chloro-5-triethylsilyl-1-pentyne” (evidently, the isomeric structure was ascribed due to mistake). Octadec-9-ynoic acid was purchased from Alfa Aesar. Dodeca-5,7-diyne 24a,3 1-hex-1-ynylcyclohexene 17a,4 were prepared as reported.

Silylation of 3-heptyn-1-ol, 6-hepten-3-yn-1-ol, was performed according to the following procedure:

Ynol and hexamethyldisilazane (1.2-1.5 equivalents per hydroxy-group) were heated neat at 80 °C for 1 h. All volatiles were removed in vacuum (1 mbar). Additional purification can be perform by a short path vacuum distillation.

Section S1. (Hept-3-ynyloxy)(trimethyl)silane (19a) O

Si

1H NMR (300 MHz, CDCl3, δ, ppm): 0.10 (s, 9 H), 0.94 (t, J = 7.4 Hz, 3 H), 1.47 (sext, J = 7.3 Hz, 2 H), 2.10 (m, 2 H), 2.35 (m, 2 H), 3.64 (t, J = 7.3 Hz, 2 H). 13C NMR (75 MHz, CDCl3, δ, ppm): -0.49, 13.45, 20.75, 22.38, 23.05, 61.81, 76.86, 81.36.

1 Tonzetich, Z. J. & Schrock, R. R. Potential Group IV olefin polymerization catalysts that contain a diamido ligand substituted with hexaisopropylterphenyl groups. Polyhedron 25, 469-476, (2006).

2 Chernichenko, K., Nieger, M., Leskelä, M. & Repo, T. Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers’ ansa-aminoborane. Dalton Trans. 41, 9029-9032, (2012).

3 Kesavan, V. & Balaraman, K. Efficient Copper(II) Acetate Catalyzed Homo- and Heterocoupling of Terminal Alkynes at Ambient Conditions. Synthesis 2010, 3461-3466, (2010).

4 Yoshida, M., Hayashi, M. & Shishido, K. Palladium-Catalyzed Diastereoselective Coupling of Propargylic Oxiranes with Terminal Alkynes. Org. Lett. 9, 1643-1646, (2007).




4

CH3

OSi

CH3

CH3

CH3

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5ppm

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

7.823.002.052.03 1.99 1.88

0.10

0.94

1.46

1.492.10

2.35

3.64

CH3

OSi

CH3

CH3

CH3

110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15 -20ppm

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Chloroform-d

-0.4

9

13.4

520.7

522.3

823

.05

61.8

1

76.8

677

.0081

.36

Section S2. (Hept-6-en-3-ynyloxy)(trimethyl)silane (25a)

OSi

1H NMR (300 MHz, CDCl3, δ, ppm): 0.11 (s, 9 H), 2.40 (m, 2 H), 2.92 (m, 2 H), 3.67 (t, J = 7.3 Hz, 2 H), 5.07 (dm, J = 10.2 Hz, 1 H), 5.29 (dm, J = 16.8 Hz, 1 H), 5.78 (m, 1 H). 13C NMR (75 MHz, CDCl3, δ, ppm): -0.49, 23.08, 23.11, 61.64, 77.90, 79.38, 115.74, 133.06.




5

CH2

OSi

CH3

CH3

CH3

6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 -1.0ppm

0.00

0.05

0.10

7.482.022.00 1.810.77 0.750.54

0.11

2.40

2.93

3.67

5.06

5.09

5.265.

32

5.78

CH2

OSi

CH3

CH3

CH3

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

Chloroform-d

-0.4

9

23.0

823

.1161

.64

77.0

077

.90

79.3

8

115.

74

133.

06

Section S3. Hept-2-ynylbenzene (14a)

Was prepared according to a modified procedure.5 A solution 2 g of hex-1-yne (24.4 mmol) in 50 ml of THF was placed into a 250 ml

Schlenk tube, cooled to -40 °C and BuLi (25 mmol, 10 ml of 2.5 M solution in hexane) was added dropwise via syringe. The bath was removed and the reaction allowed to warm up to room temperature. Then CuCl·2LiCl (3 mol %, 0.7 ml of 1 M solution in THF) was added via syringe followed by 4.18 g of benzyl bromide added via syringe as well. The reaction was left stirred over night, and then was heated for 6 h at 50 °C. After cooling down to room temperature, 20 ml of 1 M aq. HCl were added and THF was removed in vacuo. 50 ml of pentane were added, aqueous layer separated, and organic layer was washed with 10 ml of 1 M aq. HCl additionally. The residue was distilled in vacuum (1 torr), a fraction boiling at 87 °С was collected to give 2.5 g (60%) of a colourless oil.

5 Gerrard, A. F. & Djerassi, C. Mass spectrometry in structural and stereochemical problems. CLXXIX. Electron impact induced

rearrangements of 1-phenylheptenes. Further evidence for double bond lability. J. Am. Chem. Soc. 91, 6808-6814, (1969).




6

1H NMR (300 MHz, CDCl3, δ, ppm): 0.95 (t, J = 7.14 Hz, 3 H), 1.51 (m, 4 H), 2.26 (m, 2 H), 3.61 (m, 2 H), 7.24 (m, 1 H), 7.36 (m, 4 H). 13C NMR (75 MHz, CDCl3, δ, ppm): 13.61, 18.52, 21.98, 25.13, 31.13, 77.44, 82.63, 126.34, 127.81, 128.36, 137.63.

16

25

34

7 8 9 10

11 12

CH313

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

4.17 2.982.88 2.062.00

0.95

1.51

2.26

3.61

7.24

7.36

16

25

34

7 8 9 10

11 12

CH313

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Chloroform-d13

.61

18.5

221

.98

25.1

3

31.1

3

77.0

077

.44

82.6

3

126.

3412

7.81

128.

36

137.

63

Section S4. Tert-butyl(dimethyl)silyl octadec-9-ynoate (16a)

O

OSi

50 ml flask was charged with 560 mg of octadec-9-ynoic acid (2 mmol), 330 mg of tert-butyl(dimethyl)silyl chloride (2.2 mmol) and 20 ml THF. The flask was stoppered with septa, cooled in an ice bath and 0.5 ml of triethylamine were added via syringe. The reaction immersed in the cooling bath was stirred for 2 h. Then volatiles were rotavapored, the residue suspended in 10 ml of hexane and passed through 7 ml of silica gel on filter. The column was eluated with additional 40 ml of hexane, the solvent rotavapored. After drying in vacuum (1 mbar) 691 mg (87.5%) of the target compound was collected as a transparent colorless oil.




7

1H NMR (300 MHz, C6D6, δ, ppm): 0.28 (s, 6H), 0.87 (t, J = 6.9 Hz, 3H), 0.93 (s, 9H), 1.2-1.6 (m, 23H) , 2.12 (m, 6H). 13C NMR (75 MHz, C6D6, δ, ppm): -4.62, 14.32, 17.80, 19.16, 19.22, 23.05, 25.37, 25.80, 29.02, 29.16, 29.25, 29.31, 29.51, 29.55, 29.64, 29.66, 32.23, 36.02, 80.34, 80.44, 173.34.

9 8 7 6 5 4 3 2 1 0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

23.439.376.00 5.56

Benzene-d6

O

O

Si

2.5 2.0 1.5 1.0 0.5 0.0

23.43 9.376.00 5.56

2.12

1.33

0.93

0.87

0.28

1H NMR




8

200 150 100 50 0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

173.

34

80.4

480

.34

36.0

2 32.2

329

.66

29.2

525

.80

25.3

723

.05

19.1

617

.80

14.3

2

-4.6

2

O

O

Si13C NMR

Catalytic hydrogenations

Section S5. General protocol for hydrogenation in standard

conditions

0.2–0.5 mmol of an alkyne were placed into a 25 ml Schlenk tube, followed by 5 mol. % of 6 and 0.7 ml of C6D6. The tube was filled with 2–2.2 bar of hydrogen by two freeze-pump-thaw cycles and vigorously stirred at 80 °C for 3 h or longer if needed. The reaction mixture was transferred into an NMR tube and analyzed by NMR.

Section S6. Scale-up experiments

0.1-0.5 L thick walled Schlenk tube was charged with 1-10 mmol of an alkyne, precatalyst 6 (5 mol. %) and 1-20 ml of toluene. The tube was charged with 2.2 bar H2 by three freeze-pump-thaw cycles and vigorously stirred at 80 °C for the period of time stated in Table 1 (main text). In case of 15b, 18b, 20b, 21b the solvent was evaporated and the residue distilled in vacuum of oil pump (1 mbar) or water aspirator (10 mbar), depending on volatility. For 16b the solvent was evaporated and the residue was redissolved in 5 ml of hexane and flashed through SiO2 on filter (5 ml) and eluated with 40 ml of hexane, evaporated and dried in vacuum (1 mbar).

Section S7. Catalytic activity determination

Hydrogenations were performed in standard conditions as reported for catalytic hydrogentaion. The reaction was stopped prior to reaching the full conversion. High pressure hydrogentation was performed in CarlRoth Model II laboratory autoclave (250 ml/max pressure 200 bar). Hydrogen 6.0 purity was purchased from AGA and used as received.




9

In a glove box to a sample of 8 prepared from 37.5 mg of 6 (0.5 mol. % assuming 80% yield of 8) 1.060 g of hex-3-yne were added and the solution transferred into a test tube with magnetic stirrer. The tube was placed into autoclave, filled with 30 bar of H2 and the reaction was stirred at 80 °C for 15 min. The autoclave was cooled in an ice bath, H2 was vented off and the content analyzed with 1H NMR revealing 37.5% conversion into cis-hex-3-ene, corresponding to TOF=296 h-1. Table S1. Measurements of the catalytic activity.

Catalyst, mol. % Substrate Time, h T, °C Conversion, % TOF, h-1 6, 5 11a, 15a 3 80 100 >6.7 6, 2.5 11a 1 80 31 12.4 6, 5 15a 1 80 23 4.6 6, 5 15a 0.58 120 78 26.7 8, 5 15a 2.5 25 19 1.5 8, 5 15a 0.5 80 79 31.6 8, 0.5 11a 0.25 80 37.5 296[a]

[a] 30 bar H2 pressure, neat 11a.

Section S8. Attempted high-pressure hydrogenation of alkenes

11b and 12b

Alkylborane 30a was found to be stable to hydrogenolysis under standard conditions (the major component of the reaction mixture after 15 h at 80 °C under 2 bar H2). High pressure (40 bar H2) was used to check feasibility of catalytic alkenes hydrogenation. A test tube was charged with 50 mg of 6 (10 mol. %) and 90 mg of of hex-1-ene (12b) or cis-hex-3-ene (11b) and 0.5 ml of toluene-d6. The tube was placed into autoclave, filled with 40 bar of H2 and stirred at 80 °C for 15 h. The autoclave was cooled to room temperature, H2 vented off, the content of the tube transfered into a NMR tube and analyzed. In both experiments according to 19F NMR full cleavage of C6F5 groups was observed (only C6F5H was present in 19F NMR spectrum), while no hexane was found by 1H and 13C NMR. We explain this by the following relative tolerance of substituents on boron against proto-deborylation: alkenyl < C6F5 < alkyl. As result, during hydrogenation of alkenes the rate constant k2>k1 and the catalyst degradation prevails over the catalytic cycle propagation. In case of alkynes (see next paragraph) the opposite trend is observed.




10

B-

N+

R2

R1H

H

R2

R1

B

C6F5H

N

R2

R1

H

H

+

F

F

F F

F

B

N

H

C6F5

+Catalytic cyclepropagation

Catalystdegradation

k1

k2

no C6F5 group - cannot activate H2 Figure S1. In ansa-ammonium alkylborohydrides proto-deborylation of C6F5 group prevails over proto-deborylation of alkyl groups.

Section S9. Determination of maximum value of turnover number

A test tube was charged with 1.060 g of hex-3-ene and 30 mg of 6 (0.5 mol. %). The tube was placed into the autoclave, filled with 30 bar of H2 and stirred at 80 °C for 3 h. The autoclave was cooled, H2 was vented off and the content analyzed with NMR. 19F NMR revealed only C6F5H present (complete degradation of the catalyst). According to 1H NMR conversion into cis-hex-3-ene substitutes 45.5 %, which corresponds to TON=91.

B-

N+

R2

R1

H

H

H

R2

R1

H

H

28 B

C6F5H

N

R2

R1

H

H

+

F

F

F F

F

B

N

H

C6F5

+Catalytic cyclepropagation

Catalystdegradation

k1

k2

no C6F5 group - cannot activate H2 Figure S2. In ansa-ammonium alkenylborohydrides proto-deborylation of alkenyl groups prevails over proto-deborylation of C6F5 group, propagating the catalytic cycle. Proto-deborylation of 28 is a product-determining step, providing two possible pathways: the cleavage of the vinyl group, propagating the catalytic cycle, or the cleavage of the C6F5 group, the catalyst degradation process. Suggesting first order kinetics for both processes, the active catalyst amount (in any form) ceases according to C = C0e^(-k2t). The target alkene generation: dP/dt = Ck1, after integration for t=0...∞, P∞/C0 = k1/k2, equal to max turnover number, which is 91 in case of hex-3-yne as a substrate.




11

Alkenes

Section S10. (2Z)-but-2-ene (10b)

1H NMR (300 MHz, C6D6, δ, ppm): 1.51 (d, J = 4.7 Hz, 6 H), 5.48 (m, 2H). 13C NMR (125 MHz, C6D6, δ, ppm): 12.40, 124.74.

12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)

0

0.25

0.50

0.75

1.00

Nor

mal

ized

Inte

nsity

6.001.73

C6D6

C6F5H

5.48

1.52

1.50

1H NMR

CH3

CH3

220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Nor

mal

ized

Inte

nsity

C6D6

124.

74 12.4

0

13C NMR

CH3

CH3

Section S11. (2Z)-hept-2-enylbenzene (14b)

1H NMR (300 MHz, C6D6, δ, ppm): 0.87 (tm, J = 7.1 Hz, 3 H), 1.29 (m, 4 H), 2.06 (qm, J = 7.1 Hz, 2 H), 3.32 (dm, J = 7.1 Hz, 2 H), 5.48 (m, 1 H), 5.60 (m, 1 H), 7.07 (m, 1 H), 7.16 (m, 4 H). 13C NMR (75 MHz, C6D6, δ, ppm): 14.14, 22.64, 27.23, 32.17, 33.84, 126.14, 128.49, 128.68, 128.69, 130.98, 141.44. 1H NMR (300 MHz, CDCl3, δ, ppm): 0.96 (tm, J = 7.1 Hz, 3 H), 1.41 (m, 4 H), 2.19 (qm, J = 7.1 Hz, 2 H), 3.44 (d, J = 7.1 Hz, 2 H), 5.56 (m, 2 H), 7.22 (m, 3 H), 7.31 (m, 2 H).




12

13C NMR (75 MHz, CDCl3, δ, ppm): 13.98, 22.38, 26.96, 31.88, 33.49, 125.78, 127.95, 128.32, 128.37, 130.96, 141.25.

1

6

2

5

3

4

7

8

9

10

11

12CH313

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

4.393.81 3.061.951.630.76

C6F5H

1

6

2

5

3

4

7

8

9

10

11

12CH313

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm

-0.5

-0.4

-0.3

-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

14.1

422.6

4

27.2

3

32.1

733

.84

126.

1412

8.68

130.

98

141.

44

Section S12. (1Z)-but-1-enylbenzene (15b)

1H (500 MHz, C6D6, δ, ppm): 0.85 (t, J = 7.5 Hz, 3 H), 2.18 (quin, J = 7.3 Hz, 2 H), 5.51 (dt, J = 11.7 Hz, J = 7.3 Hz, 1 H), 6.35 (d, J = 11.7 Hz, 1 H), 7.02 (t, J = 7.3 Hz, 1 H), 7.13 (m, 2 H), 7.19 (d, J = 7.3 Hz, 2 H). 13C (125 MHz, C6D6, δ, ppm): 14.69, 22.39, 126.76, 128.40, 128.86, 129.11, 134.62, 138.14.




13

CH3

13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2 -3ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.001.871.29 0.69 0.68

8.0 7.5 7.0 6.5 6.0 5.5 5.0

1.29 0.69 0.680.57

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

14.6

9

22.3

9

126.

7612

8.40

129.

11

134.

62

138.

14

1

2

6

3

5

4

7

8

9

CH310

140 139 138 137 136 135 134 133 132 131 130 129 128 127 1260.0

0.5

1.0

Benzene-d6

138.

14

134.

62 129.

1112

8.86

128.

40

126.

76

Section S13. [(1Z)-5-chloropent-1-enyl](triethyl)silane (18b)

Cl

Si

1H (300 MHz, C6D6, δ, ppm): 0.63 (q, J = 7.90, 6 H, ), 0.99 (t, J = 7.90 Hz, 9 H), 1.53 (m, 2 H), 2.08 (qd, J = 7.40, J = 1.37, 2 H), 3.12 (t, J = 6.60 Hz, 2 H), 5.49 (dt, J = 14.0, J = 1.37, 1 H) 6.17 (dt, J = 14.1, J = 7.1, 1 H). 13C (75 MHz, C6D6, δ, ppm): 5.01, 7.76, 31.48, 32.80, 44.34, 126.91, 148.30;




14

Cl13 12

11

10

9

8Si1

24

6

CH33

CH35

CH37

H9a

H8a

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

9.00 6.812.33 2.292.030.89 0.85

Benzene-d6

Cl13 12

11

10

9

8Si1

24

6

CH33

CH35

CH37

H9a

H8a

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

5.01

7.76

31.4

832

.80

44.3

4

126.

91

148.

30

Section S14. 1-[(1Z)-hex-1-enyl]cyclohexene (17b)

1H NMR (300 MHz, C6D6, δ, ppm): 0.86 (t, J = 7.1 Hz, 3H), 1.32 (m, 4H), 1.51 (m, 4H), 2.01 (m, 2H), 2.13 (m, 2H), 2.28 (q, J = 7.1 Hz, 2H), 5.34 (dt, J = 11.6 Hz, J = 7.1 Hz, 1H), 5.68 (m, 1 H), 5.88 (d, J = 11.7 Hz, 1H); 13C NMR (75 MHz, C6D6, δ, ppm): 14.16, 22.54, 22.70, 23.28, 25.89, 29.03, 29.48, 32.94, 127.05, 129.73, 132.28, 135.80;




15

CH3

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5ppm

4.08 4.00 2.772.100.79 0.770.72

Benzene-d6

0.86

1.32

1.51

2.01

2.02

2.13

2.28

2.29

5.325.

36

5.68

5.86

5.90

CH3

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

Benzene-d6

14.1

6

22.5

423

.2825

.89

29.0

329

.48

32.9

4

127.

0512

9.7313

2.28

135.

80

Section S15. [(3Z)-hept-3-enyloxy](trimethyl)silane (19b)

O Si

1H NMR (300 MHz, C6D6, δ, ppm): 0.10 (d, J = 0.8 Hz, 9 H), 0.86 (t, J = 7.4 Hz, 3 H), 1.32 (sext, J = 7.1 Hz, 2 H), 1.99 (q, J = 6.5 Hz, 2 H), 2.32 (q, J = 6.3 Hz, 2 H), 3.54 (t, J = 6.9 Hz, 2 H), 5.48 (pseudo-t, J = 5.5 Hz, 2 H). 13C NMR (75 MHz, C6D6, δ, ppm): -0.38 , 13.88 , 23.16 , 29.73 , 31.46 , 62.53 , 126.43 , 131.67.




16

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5ppm

0.00

0.05

0.10

0.15

0.20

0.25

0.30

8.493.002.09 2.062.04 2.031.65

Benzene-d6

OSi

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

-0.3

8

13.8

8

23.1

6

29.7

331

.46

62.5

3

126.

43

131.

67

OSi

Section S16. Tert-butyl(dimethyl)silyl (9Z)-octadec-9-enoate (16b)

O

O

Si

1H NMR (300 MHz, C6D6, δ, ppm): 0.29 (s, 6H), 0.90 (t, J = 6.9 Hz, 3H), 0.94 (s, 9H), 1.1-1.4 (m, 21H), 1.54 (m, 2H), 2.06 (m, 4H), 2.15 (t, J = 7.4 Hz, 2H), 5.46 (m, 2H). 13C NMR (75 MHz, C6D6, δ, ppm): -4.61, 14.34, 17.81, 23.08, 25.44, 25.80, 27.62, 27.68, 29.42, 29.51, 29.59, 29.74, 29.76, 29.97, 30.11, 30.23, 32.31, 36.06, 130.10, 130.21, 173.37.




17

O

O

Si

1H NMR

12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

20.68 5.363.791.69

Benzene-d6

5.46

2.15

2.06

1.54

1.27

0.94

0.90

0.29

2.5 2.0 1.5 1.0 0.5 0.0

20.68 11.99 5.363.79 2.23

2.15

2.06

1.54

1.27

0.94

0.90

0.29

200 150 100 50 0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

173.

37

130.

10

36.0

6 32.3

129

.51

25.8

025

.44

23.0

817

.81

14.3

4

-4.6

1

13C NMR

O

O

Si

Section S17. (3Z,9Z)-dodeca-3,9-diene (20b)




18

1H NMR (300 MHz, C6D6, δ, ppm): 0.93 (t, J = 7.5 Hz, 6 H), 1.34 (m, 4 H), 2.01 (m, 8 H), 5.41 (m, 4 H). 13C NMR (75 MHz, C6D6, δ, ppm): 14.57, 20.90, 27.36, 29.71, 129.42, 131.80.

CH3

CH3

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

8.12 6.004.493.43

Benzene-d6

7.16

CH3

CH3

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

14.5

7

20.9

0

27.3

629

.71

128.

0012

9.42

131.

80

Section S18. Dodeca-5,7-diene (24b-d)

The sample was evaporated and redissolved in CDCl3 to compare with referenced values reported previously. A separate 1H NMR experiment was run with long recycle delays for precise quantification. (5Z,7Z)-dodeca-5,7-diene (24b)6

1H NMR (500 MHz, CDCl3, δ, ppm): 0.87 – 0.92 (m, 6H), 1.23 – 1.42 (m, 8H), 2.17 (q, J = 7.2, 4H), 5.41 – 5.48 (m, 2H), 6.23 – 6.27 (m, 2H). 13C NMR (125 MHz, CDCl3, δ, ppm): 14.03, 22.42, 27.25, 31.89, 123.50, 131.92.

6 M. Brichacek, L. A. Batory, J. T. Njardarson, Angew. Chem. Int. Ed. 2010, 49, 1648-1651.




19

1H NMR (500 MHz, C6D6, δ, ppm): 0.85 (t, J = 7.1 Hz, 6H), 1.29 (m, 8H), 2.15 (m, 4H), 5.46 (m, 2H), 6.39 (m, 2H). 13C NMR (125 MHz, C6D6, δ, ppm): 14.49, 23.01, 27.92, 32.54, 124.69, 132.34. (5E,7Z)-dodeca-5,7-diene (24c)

NMR data are in agreement with 7 1H NMR (500 MHz, CDCl3, δ, ppm): 0.93 (t, J = 7.2 Hz, 6H), 1.40 (m, 8H), 2.13 dt (J = 7.2, 7.2 Hz, 2H), 2.15 dt (J = 7.2, 7.2 Hz, 2H), 5.31 (dt, J = 10.8, 7.5 Hz, 1H), 5.68 (dt, J = 14.9, 7.5 Hz, 1H); 5.97 (dd, J = 10.8, 10.8 Hz, 1H), 6.33 (ddt, J = 15.1, 10.8 and 1 Hz, 1H). 13C NMR (125 MHz, CDCl3, δ, ppm): 13.98, 22.35, 27.46, 31.64, 31.98, 32.63, 125.54, 128.52, 129.93,134.51. (5E,7E)-dodeca-5,7-diene (24d)

NMR data are in agreement with 7 and 8 1H NMR (500 MHz, CDCl3, δ, ppm): 0.89 (t, J = 7.2 Hz, 6H), 1.33 (m, 8H), 2.05 (dt, J = 7.2, 7.2 Hz, 8H), 5.56 (m, 2H), 6.00 (m, 2H). 13C NMR (125 MHz, CDCl3, δ, ppm): 13.98, 22.33, 31.66, 32.33, 130.43, 132.25. (Z)-dodec-5-en-7-yne (24e)

NMR data are in agreement with 9 1H NMR (500 MHz, CDCl3, δ, ppm): 0.87-0.95 (m, 6H), 1.28-1.56 (m, 8H), 2.26-2.37 (m, 4H), 5.41-5.45 (m, 1H), 5.80 (dt , J = 10.8, 7.2 Hz, 1H); 13C NMR (125 MHz, CDCl3, δ, ppm): 13.68, 14.02, 19.29, 22.02, 22.36, 29.77, 31.04, 31.13, 77.36, 94.34, 109.26, 142.44.

7 Conn, C., Lloyd-Jones, D., Kannangara, G. S. K. & Baker, A. T. Reductive coupling of alkynes by

oxobis(diethyldithiocarbamato)molybdenum(IV)–sodium borohydride. J. Organomet. Chem. 585, 134-140, (1999).

8 Yamada, S., Ohsawa, H., Suzuki, T. & Takayama, H. Stereoselective synthesis of (E)-, (E,Z)- and (E,E)-conjugated dienes via alkylation of 3-sulfolenes as the key step. J. Org. Chem. 51, 4934-4940, (1986).

9 Chen, J. & Liu, Y. Dialkyltitanium-mediated titanation of conjugated 1,3-butadiynes and its coupling reactions with aldehydes: a facile synthesis of stereodefined enynes and trans-enynols. Tetrahedron Lett. 49, 6655-6658, (2008).




20

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Nor

mal

ized

Inte

nsity

600.00853.61253.3642.5310.4721.1610.8279.38

cis-trans

cis-cis + cis-acetylene

trans-trans

cis-trans

cis-acetylene

cis-trans

trans-trans

cis-cis

cis-trans

5.30

5.45

5.57

5.66

5.825.955.

99

6.26

6.30

CH3 CH3

15 mol. % 8,

120 C, 10 h, 2 bar H2

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2Chemical Shift (ppm)

0

0.05

0.10

Nor

mal

ized

Inte

nsity

10.4793.7221.1610.2210.829.4019.9279.389.21

cis-trans

cis-cis

trans-trans

cis-trans

cis-acetylene cis-transtrans-trans

cis-cis + cis-acetylene

cis-trans

6.30

6.26

5.99

5.95

5.82

5.66 5.

57

5.45

5.30




21

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

cis-acetylenecis-acetylene

cis-acetylene

cis-cis

cis-trans

cis-trans

cis-trans

trans-trans

cis-cis

trans-trans

cis-trans

cis-acetylene

140 135 130 125 120 115 110 105 100 95 90 85 80 75Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

cis-acetylenecis-trans

cis-cis

trans-trans

cis-trans

cis-trans

cis-trans

cis-cis

cis-acetylene

cis-acetylene cis-acetylene

Section S19. (3Z)-2-methylhexa-1,3-diene (23b)10

1H NMR (500 MHz, C6D6, δ, ppm): 0.89 (t, J = 7.5 Hz, 3 H), 1.78 (s, 3 H), 2.20 (quint, J = 7.5 Hz, 2 H), 4.92 (s, 1 H), 4.95 (s, 1 H), 5.35 (dt, J = 12.0 Hz, J = 7.5 Hz, 1 H), 5.84 (d, J = 11.7 Hz, 1 H). 13C NMR (125 MHz, C6D6, δ, ppm): 15.20, 22.69, 23.81, 115.68, 131.06, 133.88, 142.40.

Section S20. (3E)-2-methylhexa-1,3-diene (23c)10

10 Pasto, D. J., Shults, R. H., McGrath, J. A. & Waterhouse, A. Clarification of the mechanism of the reaction of terminal propargylic

chlorides with alkyl Grignard reagents. J. Org. Chem. 43, 1382-1384, (1978).




22

1H NMR (500 MHz, C6D6, δ, ppm): 0.90 (t, J = 7.1 Hz, 3 H), 1.77 (s, 3 H), 1.98 (m, 2 H), 4.89 (s, 1 H), 4.93 (s, 1 H), 5.60 (dt, J = 15.4 Hz, J = 6.8 Hz, 1 H), 6.17 (d, J = 15.8 Hz, 1 H). 13C NMR (125 MHz, C6D6, δ, ppm): 14.22, 19.20, 26.44, 114.91, 132.62, 132.93, 142.73.




23

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0Chemical Shift (ppm)

0

0.25

0.50

0.75

1.00

Nor

mal

ized

Inte

nsity

0.000.770.151.000.12

trans cistrans

cis

acetylene

cis

cis

trans

cis

acetylene

trans

acetylene

cis

acetylene

trans

cis

6.19

6.16 5.

865.

84

5.61

5.58 5.

36 5.34

5.03 4.

95 4.92

4.89

2.20

2.07

2.05

1.98

1.81

1.78

1.77

0.94

0.89

2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

Nor

mal

ized

Inte

nsity

cis

trans

acetylene

trans

cis

acetylene

trans

acetylenecis

0.89

0.90

0.94

1.77

1.78

1.81

1.982.

052.

07

2.20

6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

Nor

mal

ized

Inte

nsity

0.001.501.070.720.771.600.151.00

trans

cis

acetyleneacetylene

cis

trans

cis

4.89

4.92

4.95

5.03

5.34

5.36

5.58

5.61

5.84

5.86

CH2

CH3

CH3

CH2

CH3

CH3

CH2

CH3

CH3

15 mol. % 6,

120 C, 10 h, 2 bar H2




24

K12H08H3-gCOSY.fid.esp

6.0 5.5 5.0F2 Chemical Shift (ppm)

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

F1

Che

mic

al S

hift

(ppm

)

K12H08H3-gCOSY.fid.esp

2.5 2.0 1.5 1.0F2 Chemical Shift (ppm)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

F1

Che

mic

al S

hift

(ppm

)

gCOSY




25


0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

Nor

mal

ized

Inte

nsity

6.946.3318.9641.08100.1741.648.8320.77

trans

cis

acetylene

acetylenecis

trans

trans

cis

cis

trans

82.1

9

91.3

4

114.

9111

5.68

120.

74

128.

68

131.

06

132.

6213

2.93

133.

88

142.

4014

2.73

27 26 25 24 23 22 21 20 19 18 17 16 15 14 13Chemical Shift (ppm)

0

0.05

0.10

0.15

Nor

mal

ized

Inte

nsity

30.1313.6761.0910.3446.8458.8029.2311.97

acetylene CH2

trans

acetylene

cis

trans

CH2 cis

cis

acetylene

trans 13.5

5

14.2

214

.37

15.2

0

19.2

0

22.6

9

23.8

1

24.3

1

26.4

4

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

30.1310.3429.236.946.3318.9641.08100.1720.77

acetylene CH2

trans

acetylene

trans

CH2 cis

cis

acetylene

trans

trans

cis

acetylene

acetylene

cis

trans

trans

cis

cis

trans

13.5

514

.22

14.3

715

.20

19.2

022.6

923

.81

24.3

126

.44

82.1

9

91.3

4

114.

9111

5.68

120.

74

128.

6813

1.06

132.

62133.

88

142.

4014

2.73

CH2

CH3

CH3

CH2

CH3

CH3

CH2

CH3

CH3

15 mol. % 6,

120 C, 10 h, 2 bar H2

Section S21. (Z)-stilbene (21b)




26

1H NMR (300 MHz, C6D6, δ, ppm): 6.47 (s, 2H), 7.00 (m, 6H), 7.24 (m, 4H). 13C NMR (75 MHz, C6D6, δ, ppm): 127.37, 128.51, 129.23, 130.58, 137.67.

8.5 8.0 7.5 7.0 6.5 6.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

2.036.004.07

BENZENE-d6

6.47

7.00

7.24

165 160 155 150 145 140 135 130 125 120 115 110 105Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

BENZENE-d6

127.

37

128.

5112

9.23

130.

58

137.

67




27

Mechanistic studies

Section S22. N,N-dimethyl-2-[(pentafluorophenyl)boryl]aniline (8)

B

N

C6F5

H

Method A: 20 mg of 2-[bis(pentafluorophenyl)boryl]-N,N-dimethylaniline 6 and 0.6 ml of bromobenzene-d5 were placed into a 25 ml Schlenk tube, charged with 2.2 bar of H2 by two freeze-pump-thaw cycles and heated at 80 °C for 5 h. The reaction mixture was transferred into an NMR tube and analyzed. For measurement of 13C, 19F and 10B NMR spectra C6F5H was removed by evaporating in vacuum (1 torr, room temperature, 5 min stirring), producing a greenish solution or a greenish oil upon complete evaporation of the solvent. Method B: 150 mg of 6 (0.32 mmol) were placed into a 25 ml Schlenk tube followed by 2 ml of toluene. The tube was charged with 2.2 bar of H2 by three freeze-pump-thaw cycles and vigorously stirred for 7 h at 80 °C. Volatiles were stripped in vacuum and the residue was redissolved in a proper solvent. This method provides 8 of 80% purity based on 19F NMR and stoichiometry of subsequent reactions with different compounds. 1H NMR (300 MHz, C6D5Br, δ, ppm): 2.38 (br.s, 6 H), 4.42 (partially relaxed q., J = 105 Hz, 1 H), 6.70 (d, J = 6.7 Hz, 1 H), 7.11 (t, J = 7.7 Hz, 1 H), 7.24 (t, J = 7.2 Hz, 3 H), 7.55 (d, J = 6.8 Hz, 1 H). 13C NMR (75 MHz, C6D5Br, δ, ppm, partial): 46.23, 112.81, 126.31, 128.34, 130.46, 135.92 (dm, J = 245 Hz), 139.06 (dm, J = 235 Hz), 146.77 (dm, J = 235 Hz), 152.14. 19F NMR (300 MHz, C6D5Br, δ, ppm): -163.32 (m, 2 F, m-F), -156.78 (t, J = 20.6 Hz, 1 F, p-F), -131.74 (dd, J = 24 Hz, J = 10 Hz, 2 F, o-F). 10B NMR (53.7 MHz, C6D5Br, δ, ppm): 4.8 (br. s). 11B NMR (160 MHz, C6D6, δ, ppm): 4.5 (d, J = 105 Hz). APCI-MS+: [M+M+H]+, [C28H23B2F10N2]

+, calc.: 599.1882; found: 599.1893.




28

NCH3

CH3

B

F

F

F

F

F

H

11 10 9 8 7 6 5 4 3 2 1 0 -1 -2 -3ppm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

6.000.970.881.010.76

C6F5H

Bromobenzene-d5

Bromobenzene-d5

Bromobenzene-d57.

56 7.54

7.29 7.24

7.11 6.

716.

69

2.88

2.38

2.27

8 7 6 5 4 3 2 1 0 -1

0

0.01

0.02

6.000.970.880.98

Bromobenzene-d5

Bromobenzene-d5

C6F5H

2.27

2.38

2.88

4.42

6.69

6.71

7.11

7.24

7.29

7.54

7.56

8.0 7.5 7.0 6.5 6.0

0

0.25

0.50

0.75

1.00

0.881.010.980.76

Bromobenzene-d5

Bromobenzene-d5

Bromobenzene-d5

C6F5H

6.696.

71

7.117.

247.

29

7.54

7.56

1H NMR

N CH3

CH3

B

F

FF

F

F

H

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20Chemical Shift (ppm)

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

Bromobenzene-d5

152.

1414

8.36

145.

18

140.

5813

7.54

134.

2913

0.46

128.

3412

6.31

121.

19

112.

81

46.2

3

150 145 140 135 130 125 120 115 110Chemical Shift (ppm)

Bromobenzene-d5

Bromobenzene-d5

Bromobenzene-d5

Bromobenzene-d5

112.

81

121.

19

126.

31

128.

34

130.

46

134.

29

137.

54

140.

58

145.

18

148.

36

152.

14

13C NMR




29

NCH3

CH3

B

F

F

F

F

F

H

-110 -115 -120 -125 -130 -135 -140 -145 -150 -155 -160 -165 -170 -175 -180 -185 -190ppm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

2.180.942.00-1

31.7

4

-156

.77

-163

.33

19F NMR

NCH3

CH3

B

F

F

F

F

F

H

11B NMR

30 25 20 15 10 5 0 -5 -10 -15 -20 -25Chemical Shift (ppm)

-0.1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

4.52

20 15 10 5 0 -5 -10 -15 -20Chemical Shift (ppm)

T=80 oC

Section S23. 2-[[(Z)-1,2-Diphenylvinyl](pentafluorophenyl)boryl]-

N,N-dimethylaniline (27c)

N

B C6F5

To a sample of 8, prepared from 20 mg of aminoborane 6 in 0.6 ml of C6D5Br, 7.6 mg of diphenylacetylene 21a (1 eq.) were added. Monitoring the reaction by NMR revealed that no reaction occurred at room temperature, but at 80 °C 50% conversion was reached within 10-15 min. Under given conditions the reaction requires about 1.5 h at 80 °C to complete, producing a deep orange solution.




30

1

2

6

3

5

4

N7

B9

CH38

CH316

1729

H29a

18

1923

2022

21

3031

35

32

3433

F5C6

1H NMR (300 MHz, C6D5Br, δ, ppm): 2.54 (s, 6H, H-8,H-16); 6.71 (s, 1H, H-29); 6.72 (m, 2H, Ph); 6.81 (m, 3H, Ph, H-6); 6.88 (m, 3H, Ph); 7.05 (m, 3H, Ph); 7.19 (t, J = 7.7 Hz, 1H, H-5); 7.31 (t, J = 6.9 Hz, 1H, H-4); 7.66 (d, J = 6.9 Hz, 1H, H-3). 13C NMR (75 MHz, C6D5Br, δ, ppm, partial): 45.64 (C-8,C-16); 113.60 (C-6); 124.34 (Ph: CH); 125.64 (Ph: CH); 126.65 (Ph: 2CH); 126.89 (Ph: 2CH); 126.92 (Ph: 2CH); 127.37 (C-5); 127.85 (C-4); 128.59 (Ph: 2CH); 131.63 (C-3); 136.97 (Ph, C-quatern.); 139.13 (C-29); 143.4 (br. m, C-2); 143.70 (Ph, C-quatern.); 152.51 (C-1). 19F NMR (300 MHz, C6D5Br, δ, ppm): -163.22 (m, 2F, m-F), -156.89 (t, J = 20 Hz, 1F, p-F), -129.78 (d, J = 24 Hz, 2F, o-F). 10B NMR (53.7 MHz, C6D5Br, δ, ppm): 17.1 (br. s, ν1/2=600 Hz). APCI-MS+: [M]+, [C28H21BF5N]+, calc.: 477.1682; found: 477.1716; [M+H]+, [C28H22BF5N]+, calc.: 478.1760; found: 478.1762.

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0ppm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

6.003.102.881.040.97

C6D5Br

C6D5Br

C6D5Br

2.54

6.71

6.81

6.87

7.05

7.19

7.29

7.31

7.65

7.67

N

B

CH3

CH3

F5C6

Ph

Ph

H

8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3

0

0.1

0.2

0.3

0.4

3.103.052.722.880.060.021.040.97

C6D5Br

C6D5Br

7.67 7.65 7.

31 7.29

7.19

7.05

6.87

6.81

6.72

6.71

1H NMR




31

N

B

CH3

CH3

H

F

FF

F

F

184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0ppm

0.1

0.2

0.3

0.4

0.5

0.6

C6D5Br

C6D5Br

C6D5Br

C6D5Br

152.

51

143.

70

139.

1313

6.97

131.

6312

8.59

126.

9212

6.65

125.

6412

4.34

121.

19

113.

60

45.6

4

154 152 150 148 146 144 142 140 138 136 134 132 130 128 126 124 122 120 118 116 114 112

0.25

0.50

C6D5Br

C6D5Br

C6D5Br

113.

60

121.

19

124.

34

125.

6412

6.65

126.

9212

7.37

127.

8512

8.59

131.

63

136.

97139.

13

143.

70

152.

51

13C NMR

7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7ppm

110

115

120

125

130

135

140

ppm

CH-29

CH-6

CH, phenylsCH-5CH-4

CH-3

1

2

6

3

5

4

N7

B9

CH38

CH316

10 1729

H29a

18

1923

2022

21

3031

35

32

3433F

28

F27

F26

F25

F24

15

1413

12

11

HMQC




32

K12H01H4-gHMBC.fid.esp

7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7F2 Chemical Shift (ppm)

105

110

115

120

125

130

135

140

145

150

155

160

F1

Che

mic

al S

hift

(ppm

)

N

CH3 CH3

B

F5C6 Ph

Ph

gHMBC

N

CH3CH3

B

F

F

F

F

F

-105 -110 -115 -120 -125 -130 -135 -140 -145 -150 -155 -160 -165 -170 -175 -180ppm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

2.211.001.80

-163

.22

-156

.89

-129

.81

-129

.75

19F NMR

N

CH3CH3

B

F

F

F

F

F

140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 -160ppm

-0.1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

17.1

0

4.87

-9.6

8

10B NMR




33

Section S24. Hydroboration of enyne 23a

11%

18%

71%B

C6F5

N

S1, 11%

23a

5 eq.8, C6D6, RT

Deactivated catalyst

B

C6F5

N

B

C6F5

N

S2, 18% S3, 71%

Catalytic process propagation

H2

8 +

23b

H2, 8 - cat.in situ

B

C6F5

N

Figure. S3. Catalyst 8 hydroborates double and triple bonds of enyne 23a giving a mixture of regioisomers. 11% (at room temperature) of the catalyst is deactivated through terminal binding (product S1) at each catalytic cycle, limiting maximum turnover number to ca. 9. S1 is apparently further hydrogenated by free 8 into S4. Hydroboration of 23a with 8. In a glove box, to a stirred at room temperature solution of enyne 23a (0.215 mmol, ≥5 equivalent each) in 0.3 ml C6D6 8 (a sample prepared from 20 mg of 6) in 0.2 ml of C6D6 was added dropwise. The solution was placed into an NMR tube and analyzed by 19F and 11B NMR. The sample was further heated for 5 h at 80 °C, showing no change in 19F NMR spectrum. According to 19F NMR 8 reacts with 23a at room temperature, producing a mixture of regioisomeric products S1-S3 of double and triple bond hydroboration (Fig. S3). Product S1 substitutes 11% of the reaction mixture as evidence by similarity in spectra of S1 and S4 (which was isolated and characterized). Formation of S1-S3 is irreversible, since no change was found in product distribution upon heating at 80 °C. As result, during each catalytic cycle 11% of the catalyst is deactivated. Thus, the maximum turnover value does not exceed 9 and at least 10 mol. % of the catalyst is required for full conversion. In catalytic conditions, when 6 is heated with 5 eq. of 23a under H2 S4 is produced almost exclusively. Apparently, the triple bond in S1 is further hydrogenated catalytically into S4 with free 8. Any 8 remaining free at the end of the hydrogenation reacts with 23b to give S4 as well.

Section S25. N,N-dimethyl-2-[[(3Z)-2-methylhex-3-

enyl](pentafluorophenyl)boryl]aniline (S4)




34

6

B

C6F5

N

H2, 85 °CC6D5Br, 5h- C6F5H

S4

23b

5 eq.

23a

+ +

A 25 ml Schlenk tube was charged with 20 mg of 2-[bis(pentafluorophenyl)boryl]-N,N-dimethylaniline 6, 20 mg of 2-methylhex-1-en-3-yne 21a (5 eq.) and 1 ml of C6D5Br and filled with 2 bar H2 by two freeze-pump-thaw cycles. It was heated at 85 °C for 5 h, cooled, and the volume is reduced by half by vacuum evaporation. The residue was placed into an NMR tube and analyzed. Alternatively, the reaction was performed in C6D6 to give after complete evaporation the title compound as a colorless oil. 1H (300 MHz, C6D5Br, δ, ppm): 0.89 (t, J = 7.5 Hz, 3H), 1.01 (d, J = 6.6 Hz, 3H), 1.10 (br. s, 2H), 1.89 (m, 2H), 2.30 (s, 6 H), 2.40 (sext, J = 7.1 Hz, 1H), 5.16 (m, 2H), 6.73 (d, J = 7.7 Hz, 1H), 7.10 (t, J = 7.7 Hz, 1H), 7.23 (t, J = 7.3 Hz, 1H), 7.57 (d, J = 7.1 Hz, 1H). 13C (125 MHz, C6D5Br, partial, d, ppm): 12.93, 13.53, 19.56, 23.84, 28.88, 44.96, 112.99, 126.21, 126.60, 127.80, 130.76, 135.83 (dm, J = 240 Hz), 137.21, 138.57 (dm, J = 245 Hz), 146.48 (dm, J = 240 Hz), 151.79. 19F (282 MHz, C6D6, δ, ppm): -164.03 (m, 2F, m-F), -157.70 (t, J = 20 Hz, 1F, p-F), -132.51 (dd, J = 24 Hz, J = 9 Hz, 2F, o-F); 19F (282 MHz, C6D5Br, δ, ppm): -163.46 (m, 2F, m-F), -157.43 (t, J = 20 Hz, 1F, p-F), -132.12 (dd, J = 24 Hz, J = 9 Hz, 2F, o-F); 10B (53.7 MHz, C6D6, δ, ppm): 13.0 (br. s, ν1/2=290 Hz); APCI-MS+: [M+H]+, [C21H24BF5N]+, calc.: 396.1916; found: 396.1957.

NCH3

CH3

B

CH3

F

F

FF

F

CH3

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0ppm

2.862.382.064.582.000.880.950.94

C6D5Br

C6D5Br

C6D5Br

0.89

1.00

1.02

1.101.

89

2.30

2.40

5.16

6.716.

74

7.107.

23

7.57

7.59

1H NMR




35

NCH3

CH3

B

CH3

F

F

FF

F

CH3

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0ppm

C6D5Br

C6D5Br

C6D5Br

C6D5Br

12.9

313

.5319

.56

23.8

428.8

844.9

6

112.

99

126.

2112

6.60

127.

8013

0.76

134.

27

137.

21

140.

22

144.

87

148.

09151.

79

13C NMR

NCH3

CH3

B

CH3

F

F

FF

F

CH3

2.0 1.5 1.0ppm

10

15

20

25

30

35

40

45

50

ppm

7.5 7.0 6.5 6.0 5.5 5.0ppm

105

110

115

120

125

130

135

140

145

ppm

gHMQC




36

NCH3

CH3

B

CH3

F

F

FF

F

CH3

-16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104 -112 -120 -128 -136 -144 -152 -160 -168 -176 -184 -192ppm

2.351.172.00

-163

.46

-157

.43

-132

.15

-132

.10

19F NMR

NCH3

CH3

B

CH3

F

F

FF

F

CH3

140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 -160ppm

-0.1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

13.0

2

10B NMR

Section S26. 2-[Hexyl(pentafluorophenyl)boryl]-N,N-dimethylaniline

(30a)

N

B

C6F5 A 25 ml Schlenk tube was charged with 30 mg of 6, 8 mg of hex-1-ene (1.5 eq.), 0.6 ml of C6D6. It was then filled with 2 bar of hydrogen using two freeze-pump-thaw cycles and stirred for 4 h at 80 °C. Reaction mixture was then transferred into an NMR tube and analyzed. Removing volatiles in vacuum causes partial decomposition of the sample. Due to this the title compound was detected and characterized together with some byproduct pentafluorobenzene and excessive hex-1-ene. Extra signals of hex-1-ene were discriminated from the 1H and 13C NMR spectra by comparing with the reference spectra of hex-1-ene.




37

It should be noted, that 30a is particularly stable to hydrogenolysis: when reaction was continued for 15 h instead of 4, the title compound was the major component (>50%) of the reaction mixture. 1H (300 MHz, C6D6, δ, ppm): 0.89 (t, J = 6.6 Hz, 3H), 1.01 (pseudo-t, 2H), 1.32 (m, 4H), 1.42 (m, 4H), 2.06 (s, 6H), 6.48 (d, J = 7.7 Hz, 1H), 7.02 (t, J = 7.7 Hz, 1H), 7.19 (t, J = 7 Hz, 1H), 7.67 (d, J = 7 Hz, 1H). 13C (125 MHz, C6D6, partial, δ, ppm): 14.33, 23.18, 23.40 (m), 26.09, 32.39, 33.34, 45.95, 114.39, 127.46, 129.29, 131.62, 153.41; 19F (282 MHz, C6D6, δ, ppm): -163.90 (m, 2F, m-F), -157.94 (t, J = 20.5 Hz, 1F, p-F), -133.38 (dd, J = 25 Hz, J = 10 Hz, 2F, o-F); 10B (53.7 MHz, C6D6, δ, ppm): 12.9 (br. s, ν1/2=190 Hz); APCI-MS+: [M]+, [C20H23BF5N]+, calc.: 383.1838; found: 383.1856; [M+H]+, [C20H24BF5N]+, calc.: 384.1916; found: 384.1900.

NCH3

CH3

B CH3

F

F

F

F

F

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0ppm

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

2.333.301.560.841.040.76

1-Hexene

1-Hexene

1-Hexene

1-Hexene

1-Hexene

1-Hexene

1-Hexene

C6F5H

Benzene-d6

7.68

7.66

7.19 7.

167.

02

6.49 6.

47

2.06

1.42

1.31

1.01

0.89

8.0 7.5 7.0 6.5

0

0.05

0.10

0.841.040.970.76

6.47

6.49

7.02

7.16

7.19

7.66

7.68

2.0 1.5 1.0

0

0.1

0.2

0.3

0.4

2.333.232.133.304.254.051.566.00

1-Hexene

1-Hexene

1-Hexene

0.89

1.01

1.31

1.42

2.06

1H NMR




38

K12G12H1-HMQC.fid.esp

2.0 1.5 1.0F2 Chemical Shift (ppm)

10

15

20

25

30

35

40

45

50

F1

Che

mic

al S

hift

(ppm

)

K12G12H1-HMQC.fid.esp

7.5 7.0 6.5 6.0F2 Chemical Shift (ppm)

100

105

110

115

120

125

130

135

F1

Che

mic

al S

hift

(ppm

)

N CH3

CH3

B CH3

F

F

F

F

F

gHMQC

F

F

F

F

F

B CH3

N

CH3

CH3

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

0

0.05

0.10

0.15

0.20

Hex-1-ene

Hex-1-ene

Hex-1-ene

Hex-1-ene

C6F5H

Hex-1-ene

Benzene-d6

Hex-1-ene

153.

41 139.

15

131.

6212

9.29

128.

0012

7.46

114.

3911

4.11

100.

48

45.9

5

33.3

432

.39

26.0

923

.18

22.4

6

14.3

314

.03

13C NMR

-130 -132 -134 -136 -138 -140 -142 -144 -146 -148 -150 -152 -154 -156 -158 -160 -162 -164 -166 -168 -170 -172ppm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

2.042.440.961.182.442.00

C6F5H

C6F5H

C6F5H

-163

.90-1

57.9

4

-133

.38

F

F

F

F

F

B CH3

N

CH3

CH3

19F NMR




39

140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 -160ppm

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

12.8

8

F

F

F

F

F

B CH3

N

CH3

CH3 10B NMR

Section S27. 2-[[(1Z)-1-ethylbut-1-enyl](pentafluorophenyl)boryl]-

N,N-dimethylaniline (27b)

N

B

C6F5 Et

Et

In a 25 ml Schlenk tube to a solution of 8 in 0.5 ml of toluene (prepared from 50 mg of 6 according to method B) 30 mg of hex-3-yne (≥3.4 eq.) were added and stirred for 15 min. Volatiles were stripped in vacuum, producing 27b as a yellow oil. It was redissolved in C6D6 and analyzed by NMR. 8 was quantitatively converted into 27b. 1H (500 MHz, C6D6, δ, ppm): 0.89 (t, J = 7.4 Hz, 3H), 0.89 (t, J = 7.4 Hz, 3H), 2.10 (m, 2H), 2.16 (m, 2H), 2.24 (s, 6H), 5.86 (t, J = 7.0 Hz, 1H), 6.54 (d, J = 8.0 Hz, 1H), 7.07 (t, J = 7.7 Hz, 1H), 7.14 (t, J = 7.4 Hz, 1H), 7.65 (d, J = 7.6 Hz, 1H). 13C (75 MHz, C6D6, partial, δ, ppm): 14.27, 15.35, 22.43, 24.02, 46.06 (t, J=1.9 Hz), 114.92, 127.57, 128.69, 133.22 (t, J=3.3 Hz), 137.59 (dm, J = 250 Hz), 140.13 (dm, J = 250 Hz), 145.57, 147.19 (dm, J = 242 Hz), 154.54. 19F (282 MHz, C6D6, δ, ppm): -163.73 (ddd, J = 25.2 Hz, J = 20.6 Hz, J = 9.9 Hz, 2F, m-F), -157.71 (t, J = 20.6 Hz, 1F, p-F), -131.12 (dd, J = 25.2 Hz, J = 9.9 Hz, 2F, o-F). 11B (160 MHz, C6D6, δ, ppm): 25.2 (br. s, ν1/2=320 Hz); APCI-MS+: [M]+, [C20H21BF5N]+, calc.: 381.1682; found: 381.1720.




40

N

CH3 CH3

B

CH3

CH3

F5C6

1H NMR


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

Nor

mal

ized

Inte

nsity

5.192.370.680.680.880.71

7.65 7.

147.

076.

54

5.86

2.24

2.16 2.10

0.89




41

180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

C6D6

14.2

715

.35

22.4

324

.02

46.0

6114.

92

127.

5712

8.69

133.

2213

8.48

139.

2514

5.57

145.

7514

8.8115

4.54

150 149 148 147 146 145 144 143 142 141 140 139 138 137 136 135 134Chemical Shift (ppm)

0.025

0.050

0.075

0.100

Nor

mal

ized

Inte

nsity

135.

92

138.

48

139.

25

141.

78145.

5714

5.75

148.

81

N

CH3 CH3

B

CH3

CH3

F5C6

13C NMR




42

-88 -96 -104 -112 -120 -128 -136 -144 -152 -160 -168 -176 -184Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

1.811.192.00

-163

.72

-157

.71

-131

.15

-131

.10

N

CH3 CH3

B

CH3

CH3

F5C6

19F NMR

100 80 60 40 20 0 -20 -40 -60 -80 -100Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

25.2

0

N

CH3 CH3

B

CH3

CH3

F5C6

11B NMR

Section S28. 2-[(1-Ethylbutyl)(pentafluorophenyl)boryl]-N,N-

dimethylaniline (30c)

N

B

C6F5 Et

Et




43

Method A: In a 25 ml Schlenk tube to a solution of 8 in 0.5 ml of C6D6 (prepared from 30 mg of 6 according to method B) 20 mg of cis-hex-3-ene (≥3.8 eq.) were added and stirred for 15 min. The sample was placed into a NMR tube and 11B and 19F spectra recorded, showing complete conversion of 8 into 30c. Then volatiles were stripped in vacuum, producing 30c as a slightly greenish oil. It was dissolved in C6D6 and analyzed by 1H, 13C, 11B and 19F NMR. According to NMR 8 is was present (7 mol. %) evidencing for partial retrohydroboration of 30c upon evaporation of the solvent and excess of cis-hex-3-ene. Method B: A sample of 27b prepared as reported from 50 mg of 6 was placed into a 25 ml Schlenk tube followed by 0.5 ml of C6D6 and was filled with 2 bar of H2 by three freeze-pump-thaw cycles. The reaction was stirred for 15 h at room temperature, transferred into a NMR tube and analyzed by NMR, revealing full conversion of 27b into 30c. Method C: A 25 ml Schlenk tube was charged with 50 mg of 6 and 30 mg of hex-3-ene (3.4 eq.), 0.5 ml of toluene and 2.2 bar of H2 by three freeze-pump-thaw cycles. The reaction was vigorously stirred at 80 °C for 5 h. Volatiles were removed in vacuum, the residue was redissolved in C6D6 and analyzed by 1H, 13C, 11B and 19F NMR revealing formation of 30c as a major (>90%) product. 1H (500 MHz, C6D6, δ, ppm): 0.89 (t, J = 7 Hz, 3H), 0.97 (t, J = 7.4 Hz, 3H), 1.15-1.60 (m, 7H), 2.08 (s, 6H), 6.46 (d, J = 8.0 Hz, 1H), 7.01 (t, J = 7.0 Hz, 1H), 7.16 (t, J = 7.3 Hz, 1H), 7.59 (d, J = 7.1 Hz, 1H). 13C (75 MHz, C6D6, partial, δ, ppm): 13.37, 15.05, 22.25, 24.17, 31.91 (br. m), 33.51, 46.30 (t, J = 1.43 Hz), 113.93, 127.52, 128.98, 131.97 (t, J = 2.86 Hz), 153.11. 1H/13C gHSQC (500/125 MHz, C6D6, δ, ppm): 0.88 / 14.75; 0.96 / 13.08; 1.21 / 33.32; 1.21 / 23.97; 1.29 / 21.87; 1.34 / 29.97; 1.41 / 33.32; 1.44 / 21.87; 1.53 / 23.97; 2.08 / 46.31; 6.46 / 113.69; 7.01 / 127.46; 7.15 / 129.03; 7.59 / 131.82. 19F (282 MHz, C6D6, δ, ppm): -163.84 (ddd, J = 25.2 Hz, J = 20.6 Hz, J = 9.9 Hz, 2F, m-F), -157.74 (t, J = 20.6 Hz, 1F, p-F), -131.28 (dd, J = 25.2 Hz, J = 9.9 Hz, 2F, o-F); 11B (160 MHz, C6D6, δ, ppm): 17.15 (br. s, ν1/2=320 Hz); APCI-MS+: [M]+, [C20H23BF5N]+, calc.: 383.1838; found: 383.1852.




44

10 9 8 7 6 5 4 3 2 1 0 -1Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55N

orm

aliz

ed In

tens

ity

2.857.006.700.680.960.70

Silicone grease

0.89

0.97

2.08

6.46

7.017.

16

7.59

N

B

CH3 CH3

F5C6

CH3

CH3

2.0 1.5 1.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

Nor

mal

ized

Inte

nsity

2.853.177.006.70

2.08

0.97

0.89


0

0.025

0.050

0.075

0.100

Nor

mal

ized

Inte

nsity

0.680.960.940.70

7.59

7.16

7.01

6.46

1H NMR




45

N

B

CH3 CH3

F5C6

CH3

CH3

13C NMR


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Nor

mal

ized

Inte

nsity

Silicone grease

C6D6

153.

11

131.

9712

8.98

127.

52

113.

93

46.3

0

33.5

131

.91

24.1

722

.25

15.0

513

.37

2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9F2 Chemical Shift (ppm)

5

10

15

20

25

30

35

40

45

50

55

F1

Che

mic

al S

hift

(ppm

)

2.08, 46.31, -0.8

0.88, 14.75, -0.03

0.96, 13.08, 0.03

1.41, 33.32, 0.02 1.21, 33.32, 0.02

1.53, 23.97, 0.01 1.21, 23.97, 0.01

1.29, 21.87, 0

1.44, 21.87, 0

N

CH3 CH3

B

CH3

CH3

F5C6

gHSQC

7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4F2 Chemical Shift (ppm)

110

115

120

125

130

F1

Che

mic

al S

hift

(ppm

)

7.15, 129.03, -0.047.01, 127.46, -0.04

7.59, 131.82, -0.02

6.46, 113.69, 0




46

-96 -104 -112 -120 -128 -136 -144 -152 -160 -168 -176Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

1.691.082.00

-131

.26

-131

.31

-157

.74

-163

.84

-163

.85

N

B

CH3 CH3

F5C6

CH3

CH3

19F NMR


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

17.1

5

N

CH3 CH3

B

CH3

CH3

F5C6

11B NMR

Section S29. [2-(Dimethylammonio)phenyl](hex-1-

ynyl)bis(pentafluorophenyl)borate(1-) (31)




47

B-

C6F5

NH+

C6F5

Bu

Into a 10 ml Schlenk tube 30 mg of aminoborane 6, 20 mg of hex-1-yne (3.8 eq.) and 0.6 ml of C6D6 or CD2Cl2 were placed and stirred for 18 h at room temperature. Then volatiles were removed in vacuum, giving the title compound quantitatively as a white solid. The reaction of 6 with excess of hex-1-yne is over typically within 1 h at room temperature or 5 min at 80 °C. 1H (500 MHz, C6D6, δ, ppm): 0.78 (t, J = 7.2 Hz, 3H), 1.25 (m, 4H), 1.97 (t, J = 6.7 Hz, 2H), 2.04 (d, J = 5.7 Hz, 6H), 6.20 (d, J = 8.3 Hz, 1H), 6.83 (t, J = 7.7 Hz, 1H), 6.95 (t, J = 7.4 Hz, 1H), 7.60 (br. s, 1H), 12.61 (br. s, 1H, NH); 13C (75 MHz, C6D6, δ, ppm, partial): 13.53 (s), 19.94 (s), 22.10 (s), 31.77 (s), 45.10 (s, N+H(CH3)2), 94.70 (q, J = 65 Hz, B-C≡C-Bu), 104.13 (m, B-C≡C-Bu), 116.76 (s), 126.83 (s), 129.36 (s), 137.53 (s), 137.53 (dm, J = 240 Hz, CF), 139.14 (dm, J = 245 Hz, CF), 144.42 (s, CN+H(CH3)2), 145.87 (q, J = 53 Hz, (CH3)2HN+-CH=C-B), 148.47 (dm, J = 238 Hz, CF); 19F (282 MHz, C6D6, δ, ppm): -165.61 (m, 4F, m-F), -161.84 (t, J = 20.5 Hz, 2F, p-F), -131.93 (d, J = 24 Hz, 4F, o-F); 19F (282 MHz, CD2Cl2, δ, ppm): -165.93 (m, 4F, m-F), -162.33 (t, J = 20.5 Hz, 2F, p-F), -131.91 (d, J = 24 Hz, 4F, o-F); 10B (53.7 MHz, C6D6, δ, ppm): -20.0 (s); 10B (53.7 MHz, CD2Cl2, δ, ppm): -19.8 (s); ESI-MS-: [M-H]-, [C26H19BF10N]-, calc.: 546.1461; found.: 546.1581.

B-

CH3

N+ CH3

CH3

HF

F

F

FF

F

F

F F

F

15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm

2.743.961.860.970.950.940.92

Benzene-d6

12.6

1

7.60

6.95

6.83 6.21

2.05

1.97 1.

25

0.78

1H NMR




48

B-

CH3

N+ CH3

CH3

HF

F

F

FF

F

F

F F

F

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8ppm

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Benzene-d6

150.

0514

6.89

144.

42

140.

79

137.

5313

5.94

129.

3612

8.00

126.

83

116.

76

104.

13

95.1

694

.28

45.1

0

31.7

7

22.1

019

.94

13.5

3

160 155 150 145 140 135 130 125 120 115 110 105 100 95 90 85 80ppm

Benzene-d6

150.

05

146.

8914

5.52

144.

42

140.

7913

9.13

137.

5313

5.94

129.

3612

8.00

126.

83

116.

76

104.

13

95.1

694

.28

13C NMR

B-

CH3

N+ CH3

CH3

HF

F

F

FF

F

F

F F

F

-20 -40 -60 -80 -100 -120 -140 -160 -180ppm

3.874.00

-131

.93

-161

.84

-165

.61

-128 -130 -132 -134 -136 -138 -140 -142 -144 -146 -148 -150 -152 -154 -156 -158 -160 -162 -164 -166 -168ppm

3.871.934.00

-131

.93

-161

.84

-165

.61

19F NMR

B-

CH3

N+ CH3

CH3

HF

F

F

FF

F

F

F F

F

140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 -120 -140 -160ppm

-20.

02

10B NMR




49

Section S30. Reaction of 6 with hex-1-yne under hydrogen

A 25 ml Schlenk tube was charged with 30 mg of 6, 18 mg of hex-1-yne (3.4 eq.), 0.6 ml of C6D6. It was then filled with 2 bar of hydrogen using two freeze-pump-thaw cycles and stirred for 15 h at 80 °C. Reaction mixture was then transferred into an NMR tube to record 19F and 11B NMR spectra. Then the volatiles, including excessive hex-1-yne, were evaporated and 1H, 13C, 2D spectra were recorded. Alternatively, the hydrogenation was performed for 4h in CD2Cl2 with 30 mg of 6 and 30 mg of hex-1-yne, producing the same species in the same ratio. 1H (300 MHz, C6D6, δ, ppm): 0.87 (t, J = 7.1 Hz) + 0.91 (t, J = 7.1 Hz) + 0.93 (t, J = 7.1 Hz) = 8.8H, 1.12 (t, J = 7.1 Hz, 3.3H), 1.54 (m, 12.6H), 1.72 (m, 3H), 1.88 (m, 2.8H), 2.31 (t, J = 7.1 Hz, 1.8H), 2.39 (t, J = 7.1 Hz) + 2.41 (t, J = 6.7 Hz) = 4.5H, 2.77 (s) + 2.78 (s) = 5.5H, 2.80 (s, 2.3H), 2.96 (s) + 2.97 (s) = 4.5H, 3.01 (s, 3H), 3.18 (m, 1.5H), 3.53 (m, 1H), 6.59 (d, J = 8.2 Hz, 0.8H), 6.65 (d, J = 8.2 Hz, 2.1H), 6.87 (m, 3.1H), 7.05 (t, J = 7.3 Hz, 1H), 7.14 (m) + 7.15 (m) = 1.7H, 7.31 (t, J = 6.9 Hz, 1H), 8.00 (dd, J = 7.4, 1.7 Hz, 0.7H), 8.39 (dd, J = 7.6, 1.9 Hz, 0.9H), 8.50 (dd, J = 7.6, 1.8 Hz, 0.9H). 11B (160 MHz, CD2Cl2, δ, ppm): -3.33, 0.88, 1.89.


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

8.6412.656.2716.721.022.922.720.650.93

8.50

8.39

8.00

7.31

7.15

7.14

6.67

6.64

6.59 3.

53 3.18

3.01

2.97

2.78

2.77

2.41

2.39

2.31

1.88

1.72

1.54

1.12

0.91

0.87

8.5 8.0 7.5 7.0 6.5Chemical Shift (ppm)

2.923.112.721.010.650.93

6.59

6.64

6.67

7.05

7.147.

15

7.31

8.008.39

8.50 3.5 3.0 2.5 2.0 1.5 1.0

Chemical Shift (ppm)

8.643.3012.653.062.816.2716.721.481.02

0.87

0.91

0.93

1.12

1.54

1.72

1.88

2.31

2.39

2.41

2.77

2.78

2.80

2.96

2.97

3.01

3.18

3.53

N

CH3

CH3

B

C6F5

C6F5

+ 3.5-5 eq. CH3CH

2 bar H2, C6D6,

80 oC, 3-15 h

1H NMR




50

K12G08H4a-gHMBC.fid.esp

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0F2 Chemical Shift (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

F1

Che

mic

al S

hift

(ppm

)

gHMBC

N

CH3

CH3

B

C6F5

C6F5

+ 3.5-5 eq. CH3CH

2 bar H2, C6D6,

80 oC, 3-15 h

K12G08H4a-gHMQC.fid.esp

8.5 8.0 7.5 7.0 6.5F2 Chemical Shift (ppm)

115

120

125

130

135

140

145

F1

Che

mic

al S

hift

(ppm

)

K12G08H4a-gHMQC.fid.esp

3.5 3.0 2.5 2.0 1.5 1.0F2 Chemical Shift (ppm)

10

15

20

25

30

35

40

45

50

55

60

F1

Che

mic

al S

hift

(ppm

)

N

CH3

CH3

B

C6F5

C6F5

+ 3.5-5 eq. CH3CH

2 bar H2, C6D6,

80 oC, 3-15 h

gHMQC




51

-85 -90 -95 -100 -105 -110 -115 -120 -125 -130 -135 -140 -145 -150 -155 -160 -165 -170 -175 -180 -185 -190Chemical Shift (ppm)

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

C6F5H

C6F5H

C6F5H

-139

.57

-154

.63

-162

.89

N

CH3

CH3

B

C6F5

C6F5

+ 3.5-5 eq. CH3CH

2 bar H2, C6D6,

80 oC, 3-15 h

19F NMR

40 35 30 25 20 15 10 5 0 -5 -10 -15 -20 -25 -30 -35 -40 -45 -50 -55 -60Chemical Shift (ppm)

-0.1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

23.5930.86

-3.3

3

-0.8

8

1.89

11B NMR

N

CH3

CH3

B

C6F5

C6F5

+ 5.6 eq. CH3CH

2 bar H2, CD2Cl2,

80 oC, 4 h

Section S31. Competitive hydroboration experiments

General procedure. In a glove box, to a stirred at room temperature solution of two substrates (0.215 mmol, ≥5 equivalent each) in 0.3 ml of C6D6 a solution of 8 (a sample prepared from 20 mg of 6 according to method B) in 0.2 ml of C6D6 was added dropwise. The solution was placed into an NMR tube, analyzed by 19F, B, 1H NMR and compared with reference data. Competitive hex-3-yne vs hex-1-yne hydroboration procedure. Due to instability of hydroboration products in the presence of terminal alkynes (Fig. S4), the procedure was modified. Following the general procedure 8 was added into stirring mixture of 21.5 mg (≥6 equivalent each) of hex-1-yne and hex-3-yne in a 25 ml Schlenk tube. After 15 min of stirring at room temperature, the mixture was stirred at 80 °C for 15 min. Volatiles




52

were separated by bulb-to-bulb distillation and analyzed by 1H NMR. Hex-1-ene to cis-hex-3-ene ratio reflects the hydroboration ratio.

N

B HC6F5

N

B

C6F5

Bu

N

B

C6F5

Et

Et

NH+

B-

C6F5

Bu

NH+

B-

C6F5

Et

Et

Bu Bu

N

B

C6F5Bu

+ +

Figure S4. Competitive hydroboration of hex-3-yne vs hex-1-yne proceeds through hydroboration intermediates, which are immediately converted by excess of hex-1-yne into respective alkenes via protonative cleavage. Table 2. Cumulative results of competitive hydroboration of different alkynes and alkenes with 8

Experiment Substrate 1 Substrate 2 Ratio of products of

Substrate1 to

Substrate2

hydroboration

1

1.25:1

2

2.4:1

3

indistinguishable

4 3.1:1

5 1:8

6

1:~30

7

1:9

8

1:1.1

9 α β

α:β = 1:4




53

10

Ph Ph 1 only

Table 3. Reactivity of different alkynes and alkenes in hydroboration with 8 referenced to α–position of prop-1-yn-1-ylbenzene

Substrate and position of

hydroboration with 8

Relative rate of hydroboration at room

temperature

136

109

57

44

5.5

+

5

4

1

Ph Ph No reaction (25 °C)

No reaction (80 °C)

Section S32. Hydroboration reversibility

Hydroborane 8 (prepared from 20 mg of 6 according to method B) in 0.5 ml of C6D6 was placed into a NMR tube followed by 1 eq. of hex-1-ene (12b) or 2-methylhex-1-en-3-yne (23a) or prop-1-yn-1-ylbenzene and monitored by NMR until full conversion into hydroboration product was reached. Compound S4 was prepared as reported from 20 mg of 6. Then to the NMR tube 17.5 mg of hex-3-yne (5 eq.) were added and 1H, 19F and 11B NMR spectra recorded. The sample was heated for 5 h at 80 °C in a oil bath and analyzed by NMR. No change in spectra of the samples was found for mentioned substrates (Fig. S5).




54

80 °C, 5h

5 eq. 11a

no reactionB

C6F5

N

R2

R1

80 °C, 5h

5 eq. 11a

no reaction

S5 (R1 = Me, R2 = 4-MePh)S6 (R1= 4-MePh, R2 = Me)S5:S6=4:1 mixture

B

C6F5

N

Bu80 °C, 5h

5 eq. 11a

30a

no reaction

B

C6F5

N

S1, 11%

B

C6F5

N

B

C6F5

N

S2, 18% S3, 71%

B

C6F5

N

S4

5 eq.

80 °CC6D6, 3h

no reaction

Figure S5. Hydroboration reversibility was evaluated in attempted reactions with hex-3-yne.

Section S33. Reversibility of cis-hex-3-ene (11b) hydroboration.

To a solution of 30c (prepared from 20 mg of 6 by any of methods reported) in a NMR tube hex-3-yne (20 mg, ≥5.5 equivalents) was added and heated at 80 °C. NMR analysis (1H, 19F, 13C, 11B) revealed 26% conversion into 27b after 30 min and complete conversion after 5 h.

80 °C, 5h

5 eq.

B

C6F5

N

Et

Et

30c

+ hexenes

27b

11a

B

C6F5

N

Et

Et




55

Isotope-labelling experiments:

Section S34. 1-Methyl-4-prop-1-ynylbenzene-d3 (26a)

D

D

D

Dimethyl sulfate-d6 was prepared according to a reported procedure11 from methanol-d4 and chlorosulfonic acid; though we do not recommend to use excess of chlorosulfonic acid as stated in the original protocol. A solution of 2 g of 1-ethynyl-4-methylbenzene (17.1 mmol) in 10 ml of THF was cooled to -50 °C in a Schlenk tube and BuLi (17.2 mmol, 7.8 ml of 2.2 M solution in hexane) was added dropwise via syringe, then stirred for additional 30 min and allowed to warm up to room temperature. Then, while cooling in an ice bath, dimethyl sulfate-d6 (2.24 g, 17.5 mmol) was slowly added dropwise via syringe during 30 min. Stirring was continued for another 2 h. Then the reaction was cooled to -50 °C and additional 2 ml of BuLi (2.2 M in hexane) were added dropwise via syringe, the reaction was left stirring over night immersed in the cooling bath allowing to warm up to room temperature naturally. Then 2 ml of conc. aq. NH3 were added and stirred for 12 h. The reaction mixture was distributed between 50 ml of hexane and 40 ml of water, transferred to a separatory funnel, organic phase separated and the aqueous one was extracted additionally with 20 ml of hexane. Organic extracts were combined, dried over Na2SO4, evaporated, and distilled (in vacuum of a water aspirator pump) to give crude material as a yellowish liquid, boiling at 80 °C. It was redistilled again to give 1.1 g (48%) of colorless oil. 1H NMR (300 MHz, CDCl3, δ, ppm) 2.33 (s, 3 H), 7.09 (d, J = 8.1 Hz, 2 H), 7.30 (d, J = 8.1 Hz, 2 H). 13C NMR (75 MHz, CDCl3, δ, ppm, partial): 21.32, 79.78, 84.83, 120.93, 128.91, 131.32, 137.41. 2H NMR (MHz, C6H6, δ, ppm): 1.62 (s)

11 Morse, A. T., Massiah, T. F. & Leitch, L. C. Organic Deuterium Compounds: Xxi. Synthesis of Deuterated Azobismethane. Can. J.

Chem. 37, 1-3, (1959).




56

4

5

3

6

2

1CH37

8 9 10

D11

D12

D13

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.001.831.76

Chloroform-d

2.33

7.08

7.107.

287.

31

4

5

3

6

2

1CH37

8 9 10

D11

D12

D13

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Chloroform-d

21.3

2

79.7

8

84.8

3

120.

93

128.

9113

1.32

137.

41

4

5

3

6

2

1CH37

8 9 10

D11

D12

D13

12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

1.62

7.16

2H NMR

Section S35. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d3 (26b)




57

D

DD

H

H

Was prepared by hydrogenation of 33 mg of 1-methyl-4-prop-1-ynylbenzene-d3 under standard conditions (2.2 bar of H2, 0.7 ml of C6D6 at 80 °C during 3h with 5.8 mg of 6 (5 mol %). The reaction mixture was analyzed by NMR as is. 1H (300 MHz, C6D6, δ, ppm): 2.13 (s, 3H), 5.63 (d, J = 11.5 Hz, 1H, Tol-CH=CH-CD3), 6.45 (d, J = 11.5 Hz, 1H, Tol-CH=CH-CD3), 7.01 (dm, J = 7.9 Hz, 2H), 7.20 (dm, J = 8.2 Hz, 2H); 13C NMR (125 MHz, CDCl3, δ, ppm, partial): 21.10, 125.82, 129.13, 129.18, 130.47, 135.25, 136.11. 2H (76.7 MHz, C6H6, δ, ppm): 1.68 (d, J = 1.26 Hz, 3D).

CH3

H H

DD

D

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.022.052.01 1.00 0.99

Benzene-d6

2.13

5.615.65

6.43

6.47

6.99

7.02

7.18

7.20




58

CH3

H H

DD

D

230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Benzene-d6

21.1

0

125.

8212

9.13

130.

47

135.25136.11

140 135 130 125 120

-0.10

-0.05

0.00

0.05

0.10

Benzene-d6

136.11

135.25

130.

47

129.

1812

9.13

125.

82

130.0 129.5 129.0 128.5

0.0

0.5

1.0

129.

1812

9.13

2H NMR

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

C6D6

7.16

1.69 1.

67

CH3

H H

DD

D

Section S36. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d5 (26c)

D

DD

D

D

Was prepared by deuterogenation (2.2 bar of D2) of 33 mg of 1-methyl-4-prop-1-ynylbenzene-d3 with 11.6 mg of 6 (10 mol %) in 0.7 ml of C6D6 at 80 °C during 5h. The reaction mixture was analyzed by NMR as is.




59

1H (300 MHz, C6D6, δ, ppm): 2.13 (s, 3H), 7.01 (dm, J = 7.9 Hz, 2H), 7.20 (dm, J = 8.2 Hz, 2H); 13C (125 MHz, CDCl3, partial, δ, ppm): 21.10, 129.13, 129.17, 135.20, 136.11; 2H (76.7 MHz, C6H6, δ, ppm): 1.68 (s, 3D), 5.62 (s, 1D), 6.45 (s, 1D).

4

5

3

6

2

1

CH37

8

10

12D13

D14

D15

D9

D11

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.001.661.48

Benzene-d6

2.13

6.99

7.02

7.16

7.18

7.21

4

5

3

6

2

1

CH37

8

10

12D13

D14

D15

D9

D11

160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Benzene-d6

21.1

0

128.

0012

9.13

129.

17

135.

2013

6.11

CH3

D

D

D

D

D

2H NMR

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.001.01 0.98

C6D6

7.16

6.45

5.62

1.68




60

Section S37. Hydrogenation of 1-methyl-4-prop-1-ynylbenzene-d3

with HD.

Was performed similar to hydrogenation, starting from 33 mg of 1-methyl-4-prop-1-ynylbenzene-d3 under standard conditions (0.7 ml of C6D6 at 80 °C during 3h with 5.8 mg of 6 (5 mol. %) but using HD (1.2 bar). The reaction reached only 60% conversion after 3 h due to low pressure of available HD. The reaction mixture was exposed to air to decrease relaxation time. The reaction mixture was analyzed by NMR using at least 30 s recycle delays for precision quantification. Based on the data collected the mixture comprising: Table 4. Products distribution of the 1-methyl-4-prop-1-ynylbenzene-d3 catalytic hydrogenation with HD based on 1H and 2H NMR.

Isotopomeric styrene Content based on 1H NMR

Content based on 2H NMR

D

D D

H

H

24

D

D D

D

D

26.5

D

D D

H

D

18.4

D

D D

D

H

31.1

D

D D

D

H D

D D

D

D

57.6 57

D

D D

H

D D

D D

D

D

44.9 43




61

CH3

D

DD

H D

CH3

H H

DD

D

CH3

D D

DD

D

CH3

H D

DD

D

CH3

D H

DD

D

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0ppm

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

300.00204.47 55.0818.41

Benzene-d6

2.00

2.13

5.63

6.43

6.45

6.47

6.826.846.

997.

027.

167.18

7.217.

407.

43

7.5 7.0 6.5 6.0 5.5

0.0

0.1

0.2

204.47200.46 55.0818.41

Benzene-d6

7.43 7.

40

7.21

7.18

7.16 7.

026.

99

6.84

6.82

6.47

6.45 6.43

5.63

6.60 6.55 6.50 6.45 6.40 6.35

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

18.41 12.5011.49

6.47

6.45 6.43

CH3

D

DD

H D

CH3

H H

DD

D

CH3

D D

DD

D

CH3

H D

DD

D

CH3

D H

DD

D

2H NMR

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

300.0056.94 42.97

C6D6

7.16

6.44

5.62

1.68

1.62

Section S38. Stoichiometric reaction of the catalyst 8 with the

model substrate 26a and subsequent treatment with D2.




62

BH

N

C6F5

8

CD3

B

N

C6F5

H

CD3

B

N

C6F5

HCD3

79 : 21

D

H

CD3

H

D

CD3

+

+

+D2 -B

N

C6F5

D

79 : 21 Figure S6. Reaction of 1-methyl-4-prop-1-ynylbenzene-d3 with equimolar amount of 8 followed by treatment with D2. This experiment was performed in two separate runs: in the first one (Experiment A) 8 was treated with excess of 27 to insure full conversion of 8 into hydroboration regioisomers in a ratio 79:21, which were characterized by various spectroscopic methods. In the second run (Experiment B) 8 was taken in excess to 27 to avoid presence of excessive 27. Otherwise the reaction would run in a catalytic rather than stoichiometric fashion, converting excessive 27 into D-D hydrogenated product, spoiling the picture of exclusive H-D product formation observed in a stochiometric mode.

Section S39. Experiment A:

12 mg of 1-methyl-4-prop-1-ynylbenzene-d3 (90 mkmol) were placed into an NMR tube followed by a solution of 8 (prepared from 30 mg of 6, ≥64.5 mkmol) in 0.5 ml C6D6. NMR analysis performed after 20 min revealed full consumption of 8 and formation of two regioisomeric hydroboration products in a ratio 79:21.

Section S40. N,N-dimethyl-2-[[(Z)-1-methyl-2-(4-

methylphenyl)vinyl](pentafluorophenyl)boryl]aniline-d3 (27d)

N

BC6F5

CD3

1H (500 MHz, C6D6, δ, ppm): 2.11 (s, 3H), 2.23 (s, 6H), 6.51 (d, J = 8.0 Hz, 1H), 6.91 (s, 1H), 6.99 (d, J = 7.7Hz, 2H), 7.05 (t, J = 7.7 Hz, 1H), 7.20 (d, J = 8 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 7.76 (t, J = 7.1 Hz, 1H). 2H (77 MHz, C6D6, δ, ppm): 1.97 (s). 13C (75 MHz, C6D6, partial, δ, ppm): 21.12, 46.05 (t, J = 2.1 Hz), 114.67, 128.25, 128.91, 128.98, 129.60, 133.03 (t, J = 3.8 Hz), 135.98, 137.00, 137.67 (dm, J = 245 Hz), 139.69, 140.09 (dm, J = 245 Hz), 147.35 (dm, J = 240 Hz), 153.77.




63

19F (282 MHz, C6D6, δ, ppm): -163.57 (ddd, J = 25 Hz, J = 20.6 Hz, J = 9 Hz, 2F, m-F), -157.84 (t, J = 20.6 Hz, 1F, p-F), -130.56 (dd, J = 25 Hz, J = 9 Hz, 2F, o-F); 11B (160 MHz, C6D6, δ, ppm): 18.1 (br. s); APCI-MS+: [M]+, [C24H18D3BF5N]+, calc.: 432.1871; found: 432.1830.

Section S41. N,N-dimethyl-2-[[(1Z)-1-(4-methylphenyl)prop-1-

enyl](pentafluorophenyl)boryl]aniline-d3 (27e)

N

BC6F5 CD3

1H (500 MHz, C6D6, δ, ppm, partial): 2.13 (s, 3H), 2.22 (s, 6H), 6.51 (s, 1H), 6.59 (d, J = 8.2 Hz, 1H), 6.67 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 7.7 Hz, 2H), 7.72 (d, J = 6.9 Hz, 1H). 2H (77 MHz, C6D6, δ, ppm): 1.44 (br. s). 13C (75 MHz, C6D6, partial, δ, ppm): 21.05, 46.33 (t, J = 1.6 Hz), 114.80, 128.47, 128.61, 128.66, 133.20 (t, J = 3.3 Hz), 134.51, 138.62, 154.04. 19F (282 MHz, C6D6, δ, ppm): -164.15 (ddd, J = 25 Hz, J = 20.6 Hz, J = 9 Hz, 2F, m-F), -157.89 (t, J = 20.6 Hz, 1F, p-F), -130.56 (dd, J = 25 Hz, J = 9 Hz, 2F, o-F); 11B (160 MHz, C6D6, δ, ppm): 15.5 (br. s); APCI-MS+: [M]+, [C24H18D3BF5N]+, calc.: 432.1871; found: 432.1830.




64

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

8.113.30 1.181.00 0.92 0.15

B

C

A

B B

B

C

B

AB

C

B

C

C

B

B

A

C

7.76

7.20

7.19

7.05 6.

986.

91

6.51

2.23

2.11

1H NMR

N

B

C6F5

CD3CD3

N

B

C6F5CD3

A

BC

8.0 7.5 7.0 6.5 6.0

0.00

0.05

0.10

0.15

3.30 2.15 1.181.00 0.92 0.47 0.18 0.15

B

C

A

B

B

B C B

A C

B

C

B

C

7.76

7.20

7.19

7.05

6.98

6.91

6.51

2.3 2.2 2.1 2.0

7.08 3.002.04

BC

C

B

A

2.23

2.11




65

N

B

C6F5

CD3

CD3

N

B

C6F5CD3

2H NMRA

B

C

9 8 7 6 5 4 3 2 1

0.00

0.01

0.02

0.03

79.41

Benzene-d6

B CA

1.97

1.62

1.44

2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1

0.00

79.71 49.06 20.29

B A

C

1.97 1.62

1.44




66

N

B

C6F5

CD3CD3N

B

C6F5CD3

A

BC

13C NMR


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

C

BB

B

B

C

B

A

A

B

C

C

C

B

C

B

C

B

A

B

C


BC A

B

B

C C

BA

B

A

B

B

C

C

C

B

C6D6




67

N

B

C6F5

CD3N

B

C6F5CD3B

C

-120 -125 -130 -135 -140 -145 -150 -155 -160 -165 -170Chemical Shift (ppm)

0

0.25

0.50

0.75

1.00

Nor

mal

ized

Inte

nsity

44.8097.46195.82

-130

.53

-130

.59

-157

.84

-157

.89

-163

.56 -1

63.5

8-1

64.1

5-1

64.1

6

-157.5 -158.0 -158.5 -159.0 -159.5 -160.0 -160.5 -161.0 -161.5 -162.0 -162.5 -163.0 -163.5 -164.0 -164.5Chemical Shift (ppm)

44.80155.2597.46

B

C

B

C-157

.84

-157

.89

-163

.56

-163

.58

-164

.15

-164

.16

19F NMR




68

11B NMR

N

B

C6F5

CD3N

B

C6F5CD3B

C

100 50 0 -50 -100

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

BC

18.1

315

.49

Section S42. Experiment B:

7 mg of 1-methyl-4-prop-1-ynylbenzene-d3 (52.5 mkmol) were placed into a 25 ml Schlenk tube followed by a solution of 8 (prepared from 50 mg of 6, ≥107 mkmol) in 0.5 ml C6D6. The reaction was stirred at room temperature for 2 h, then filled with 2 bar D2 by three freeze-pump-thaw cycles and stirred at room temperature for 15 h. The mixture was then passed through a short column with SiO2 (2 ml) and eluated with hexane. The solvent evaporated and analyzed by 1H NMR. The sample was then evaporated, redissolved in C6H6 and analyzed by 2H NMR. Two isotopomeric 1-methyl-4-[(1Z)-prop-1-enyl]benzenes-d4 were formed in a ratio 79:21. This ratio is similar to the ratio of regioisomers produced upon hydroboration step and evidence for selective deutero-deborylation. No evidence of H-H or D-D species formation was found.

Section S43. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d4 (26e)

D

DD

D

H

1H (500 MHz, C6D6, δ, ppm): 2.13 (s, 3H), 5.63 (s, 1H), 7.01 (dm, J = 7.9 Hz, 2H), 7.20 (dm, J = 8.2 Hz, 2H); 2H (76.7 MHz, C6H6, δ, ppm): 1.68 (s, 3D), 6.46 (d, J = 1.68 Hz, 1D)

Section S44. 1-Methyl-4-[(1Z)-prop-1-enyl]benzene-d4 (26d)

D

DD

H

D




69

1H (500 MHz, C6D6, δ, ppm): 2.13 (s, 3H), 6.45 (s, 1H), 7.01 (dm, J = 7.9 Hz, 2H), 7.20 (dm, J = 8.2 Hz, 2H); 2H (76.7 MHz, C6H6, δ, ppm): 1.68 (s, 3D). 5.63 (d, J = 1.68 Hz, 1D).

D

CD3

H

1H NMR H

CD3

D

8 7 6 5 4 3 2 1 0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.032.01 0.79 0.21

Benzene-d6

hexane

hexane

7.19

7.00

6.46

5.63

2.13

7.5 7.0 6.5 6.0 5.5

0.00

0.05

0.10

0.15

2.011.98 0.79 0.21

Benzene-d6

7.19

7.00

6.46

5.63




70

D

CD3

H

2H NMR H

CD3

D

6.5 6.0 5.5

9 8 7 6 5 4 3 2 1 0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3.000.790.21

benzene

6.46

5.62

1.68

Section S45. [(Z)-2-phenylvinyl]benzene-d1 (21c)

BH

N

C6F5

8

B

N

C6F5

D

H DPhPhN

B

C6F5 Ph

Ph

HD2

+

A sample of 8 prepared according to the method B from 50 mg of 6 (ca. 0.086 mmol) in 1 ml of toluene was placed into a Schlenk tube followed by 9.5 mg of diphenylacetylene (0.053 mmol). The reaction was stirred for 2 h at 80 °C to insure complete hydroboration of diphenylacetylene. The Schlenk tube was charged with 2 bar of D2 by three freeze-pump-thaw cycles and stirred for 20 min at 80 °C. Then volatiles were stripped in vacuum, the residue dissolved in C6D6 and analyzed by 1H, 19F NMR. Afterwards the solvent was evaporated and the sample redissolved in C6H6 and analyzed by 2H NMR. Eventually, the sample was passed through short column (2 ml SiO2) first in 1:1 toluene-hexane mixture and evaporated. The sample collected was passed through another short column (2 ml SiO2) in hexane. A produced sample of stilbene-d was analyzed by 1H, 2H, 13C NMR and EI-MS. Some trans-stilbene (5 mol. %) was detected by 13C NMR, though no evidence of trans-stilbene-d was found in 2H NMR spectrum. Perhaps, it was produced in side reaction, for example, as result of thermal dismutation of 27c. 1H (500 MHz, C6D6, δ, ppm): 6.47 (s, 1H), 6.99 (m, 6H), 7.24 (m, 4H). 2H (77 MHz, C6H6, δ, ppm): 6.46 (d, J = 1.68 Hz). 13C (125 MHz, C6D6, partial, δ, ppm): 127.36, 127.37, 128.50, 128.51, 129.22, 129.23, 129.27, 130.23 (t, J = 23.7 Hz), 130.45, 137.58, 137.68 (t, J = 1.3 Hz). EI-MS+: [M]+, [C14H11D]+, calc.: 181.1; found: 181 (100%), 180 (100%), 179 (78%), 178 (23%), 182 (16%).




71

EI-MS: the pattern of the molecular peak multiplet of 21c (H-D-stilbene) was essentially the same as the one of 21b (H-H-stilbene), except +1 higher e/z ratio. Since the pattern includes [M-2H] peaks, the identity of the patterns can be explained by the MS dehydrogenation process involving formation of phenanthrenic rather than diphenylacetylenic spesies.

11 10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

1.241.00

Benzene

8-d

6.47

6.44

4.57

D

2H NMR

N

B

C6F5

CH3

CH3

D

N

B

C6F5

CH3

CH3

Ph

Ph

D2




72

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

1.036.004.02

C6D6

D

1H NMR

7.0 6.5Chemical Shift (ppm)

1.036.004.02

C6D6

7.25

7.23

7.01 6.99

6.47

D

2H NMR

10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

Benzene

7.33

6.47

6.45


0

0.25

0.50

0.75

1.00

Nor

mal

ized

Inte

nsity

6.47

6.45




73

D


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Nor

mal

ized

Inte

nsity

0.230.234.070.111.010.21

toluene

trans-stilbene

cis-H-H-stilbene

trans-stilbene

trans-stilbene

C6D6

trans-stilbene

toluene

137.

8313

7.79

137.

6913

7.68

137.

6713

7.58

130.

4513

0.23

129.

2712

9.23

129.

22

128.

5112

8.50

127.

3712

7.36

13C NMR

138.1 138.0 137.9 137.8 137.7 137.6 137.5 137.4Chemical Shift (ppm)

0

0.025

0.050

Nor

mal

ized

Inte

nsity

0.210.270.030.06

toluene

137.

83

137.

79

137.

6913

7.68

137.

67

137.

58

130.0 129.5 129.0 128.5 128.0 127.5Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

Nor

mal

ized

Inte

nsity

1.984.060.240.114.020.330.94

trans-stilbene

trans-stilbene

C6D6

130.

45

130.

23

129.

2712

9.23

129.

22

128.

5112

8.50

127.

37




74

PFC - reference

HH

EI-MS+: cis-stilbene reference

HD

EI-MS+: cis-stilbene-d




75

Section S46. 2-[(1-ethylbutyl)(pentafluorophenyl)boryl]-N,N-

dimethylaniline-d2

N

B

C6F5 Et

EtD

D

N

B

C6F5 Et

Et

D D

N

B

C6F5 Et

Et

H

N

B HC6F5

D2N

B

C6F5

Et Et

H D

D+

27b

Figure 7. Reaction of hex-3-yne with equimolar amount of 8 followed by D2 results in formation of two deuterated hex-3-yl boranes. They originate from hydroboration of cis-hex-3-ene-d formed in situ with 8. A solution of 27b (prepared from mg 30 mg of 6 as reported) in 0.5 ml of C6D6 was placed into a 25 ml Schlenk tube and charged with 2 bar of D2 by three freeze-pump-thaw cycles. After stirring for 15 h at room temperature the solution was transferred into an NMR tube and analyzed by 1H, 19F, 11B, 13C NMR. Then the solvent was removed in vacuum, the residue redissolved in C6H6 and analyzed by 2H NMR. 11B and 19F NMR did not reveal any difference from 30c. 2H and 1H NMR were consistent with formation of deuterated species, but were not informative enough due to coupling and overlapping of signals. The most informative was 13C NMR: while chemical shifts of the catalysts core were similar to 30c, hex-3-yl-d2 shifts were different (due to isotopic effect), revealing the presence of two species different from 30c in ca. 1:1 ratio (Fig. 7). In addition, a characteristic CHD signal was detected in 13C spectrum (δ = 32.99 ppm).

N

BC6F5 Et

EtD

D

N

BC6F5 Et

Et

D D 1H (500 MHz, C6D6, δ, ppm): 0.88 (t, J = 7 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H), 1.15-1.60 (m, 5H), 2.10 (s, 6H), 6.46 (d, J = 7.7 Hz, 1H), 7.01 (t, J = 7.7 Hz, 1H), 7.16 (t, J = 7.4 Hz, 1H), 7.59 (d, J = 7.1 Hz, 1H). 2H (77 MHz, C6H6, δ, ppm): 1.02 (s), 1.15 (s), 1.34 (s), 1.52 (m). 13C (75 MHz, C6D6, partial, δ, ppm): 13.31, 13.36, 15.00, 15.03, 22.06, 22.09, 24.04, 24.14, 31.78 (br. m), 32.99 (t, J = 18.9 Hz), 46.32 (t, J = 1.43 Hz), 113.97, 127.55, 128.98, 131.94 (t, J = 2.8 Hz), 137.55 (dm, J = 250 Hz), 139.93 (dm, J = 250 Hz), 147.38 (br. m), 147.56 (dm, J = 240 Hz) , 153.14. 19F (282 MHz, C6D6, δ, ppm): -163.85 (ddd, J = 25.2 Hz, J = 20.6 Hz, J = 9.9 Hz, 2F, m-F), -157.79 (t, J = 20.6 Hz, 1F, p-F), -131.23 (dd, J = 25.2 Hz, J = 9.9 Hz, 2F, o-F); 11B (160 MHz, C6D6, δ, ppm): 17.05 (br. s, ν1/2=320 Hz); APCI-MS+: [M]+, [C20H21D2BF5N]+, calc.: 385.1964; found: 385.1957.




76

1H NMR

N

CH3 CH3

B

CH3

CH3

F5C6

D

D

N

CH3 CH3

B

CH3

CH3

F5C6

DD

10 9 8 7 6 5 4 3 2 1 0 -1Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Nor

mal

ized

Inte

nsity

2.875.746.00

0.88

0.96

2.10

6.48

7.01

7.16

7.57


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

Nor

mal

ized

Inte

nsity

C6D613

.36

15.0

3

22.0

9

24.1

431

.78

32.9

9

46.3

2

113.

97

127.

5512

8.98

131.

9413

8.27

141.

5814

6.03

149.

1415

3.14




77

34 32 30 28 26 24 22 20 18 16 14Chemical Shift (ppm)

0.05

0.10

0.15

0.20N

orm

aliz

ed In

tens

ity

32.9

9

31.7

8

24.1

424

.04

22.0

922

.06

15.0

315

.00

13.3

613

.31


0

0.05

0.10

0.15

0.20

Nor

mal

ized

Inte

nsity

C6D6

153.

14

149.

14

147.

38

146.

03

141.

58

139.

23

138.

27

135.

86

131.

94

128.

98

127.

55

2H NMR

N

CH3 CH3

B

CH3

CH3

F5C6

D

D

N

CH3 CH3

B

CH3

CH3

F5C6

DD

13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1Chemical Shift (ppm)

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

0.050

0.055

Nor

mal

ized

Inte

nsity

Benzene

1.02

1.15

1.34

1.52




78

-88 -96 -104 -112 -120 -128 -136 -144 -152 -160 -168 -176 -184 -192Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0N

orm

aliz

ed In

tens

ity

1.831.012.00-1

31.2

1-1

31.2

6

-157

.79

-163

.86

19F NMR

N

CH3 CH3

B

CH3

CH3

F5C6

D

D

N

CH3 CH3

B

CH3

CH3

F5C6

DD

N

CH3 CH3

B

CH3

CH3

F5C6

D

D

11B NMR

N

CH3 CH3

B

CH3

CH3

F5C6

DD


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Nor

mal

ized

Inte

nsity

17.0

5




79

Section S47. Details of attempted catalytic hydrogenation with

(C6F5)2BH and (C6F5)3B

Our attempts to realize approach depicted at Fig. 1b (main text) using (C6F5)2BH together with dialkylanilines and additives were unsuccessful (Table S4). Sterically hindered 2,2,6,6-tetramethyl-1-phenylpiperidine was found to be frustrated with (C6F5)2BH and used as a base due to its lower basicity comparing to N-alkyl-TMP derivatives. Another direction was essentially the same as reported recently by Greb et. al.12 – to use weakly basic Lewis base (PhNMe2) to promote protonation of alkenes by hydrogen adduct [PhNMe2H]+[HB(C6F5)3]

-. Table S4. Early unsuccessful attempted hydrogenations of alkenes and alkynes under 2 bar H2 pressure. Substrate Catalyst Conditions (+)-β-citronellene

(C6F5)2BH, 5 mol % PhTMP,[a] 5 mol % [PhTMPH]+[B(C6F5)4]

-,[b] 5%

80 °C, C6D6, 18 h

Trans-Stilbene

PhPh

B(C6F5)3, 10%; PhNMe2, 10% [PhNMe2H]+[B(C6F5)4]

-, 5%

50 °C, CH2Cl2, 55 h

Hex-3-yne

(C6F5)2BH, 10 mol % PhTMP, 10 mol %

80 °C, C6D6, 18 h

[a] 2,2,6,6-Tetramethyl-1-phenylpiperidine was isolated as a byproduct during preparation of 1-(2-iodophenyl)-2,2,6,6-tetramethylpiperidine, the starting material for the preparation of 6. See K. Chernichenko, M. Nieger, M. Leskelä, T. Repo, Dalton Trans. 2012, 41, 9029; [b] This salt was prepared by a metathesis between PhTMP and [PhNMe2H]+[B(C6F5)4]

-. Both compounds were stirred in CH2Cl2, then volatiles were stripped in vacuum, including PhNMe2.

Importantly, in attempt to prepare borenium cation salt [(C6F5)2BNMe2Ph]+[B(C6F5)4]

-, we have found that (C6F5)2BH and B(C6F5)3 remain intact in the presence of [PhNMe2H]+[B(C6F5)4]

-.

BH

C6F5

C6F5

+

H+

NBC6F5

C6F5 N+[B(C6F5)4]- + H2

B

C6F5

C6F5

+

H+

NBC6F5

C6F5 N+[B(C6F5)4]- + C6F5H

[B(C6F5)4]-

C6F5

intact

[B(C6F5)4]-

12 Greb, L. et al. Metal-free catalytic olefin hydrogenation: low-temperature H2 activation by frustrated Lewis pairs. Angew. Chem. In. Ed. 51, 10164-10168 (2012).




80

Hence, we tried anilinium salts with weakly coordinating anions as additional Brønsted acidic promoters to force the protonation of substrate, the key step in the hydrogenation of unsaturated hydrocarbons. In case of (C6F5)2BH the respective salt [PhTMPH]+[B(C6F5)4]

- was used as acidic promoter, prepared by metathesis between PhTMP and [PhNMe2H]+[B(C6F5)4]

-.




81

Computational Protocol

In the present study, density functional theory with the dispersion-corrected, range-separated hybrid ωB97X-D exchange-correlation functional13 was employed to examine possible reaction pathways relevant to the title reaction. For geometry optimizations, the 6-311G(d,p) polarized triple-ζ basis set was used, however, additional single-point energy calculations were carried out for each located stationary point with the larger 6-311++G(3df,3pd) basis set.14 To ensure the accuracy of numerical integrations, the ultra-fine integration grid was employed in all electronic structure calculations.

The nature of the stationary points was characterized via vibrational analysis. The initial structures for transition state (TS) calculations were determined via potential energy surface scan calculations with respect to selected internal coordinates, which were then followed by TS optimizations. For all transition states, intrinsic reaction coordinate (IRC) calculations were performed using a Hessian-based predictor-corrector algorithm.15 The harmonic frequencies were computed at the ωB97X-D/6-311G(d,p) level. These data were also utilized to estimate the zero-point energies as well as the thermal and entropic contributions to the Gibbs free energies. The thermochemical data were obtained within the ideal gas – rigid rotor – harmonic oscillator approximation for T = 298.15K and p = 1 atm, however, concentration correction (0.00302 a.u.) was applied to Gibbs free energies corresponding to c = 1 mol/dm3 condition in solvent phase. The solvent effects were also taken into account at the ωB97X-D/6-311G(d,p) level by estimating the solvation free energies (solvent=benzene) by using the integral equation formalism variant of the polarizable continuum model (IEFPCM).16 The atomic radii and non-electrostatic terms in the IEFPCM calculations were those introduced recently by Truhlar and coworkers (SMD solvation model).17

The energy values reported in the paper correspond to solution phase Gibbs free energies that are based on ωB97X-D/6-311++G(3df,3pd) electronic energies and all additional terms obtained at the ωB97X-D/6-311G(d,p) level (see Table С1 in Section S52). All DFT calculations were carried out with the Gaussian 09 software.18

13 a) Chai, J.-D. & Head-Gordon, M. Long-range corrected hybrid density functionals with damped atom–atom dispersion

corrections. Phys. Chem. Chem. Phys. 10, 6615, (2008). b) Chai, J.-D. & Head-Gordon, M. Systematic optimization of long-range corrected hybrid density functionals. J. Chem. Phys. 128, 084106, (2008). c) Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787-1799, (2006).

14 For the 6-311G(d,p) and 6-311++G(3df,3pd) basis sets, see: a) Krishnan, R., Binkley, J. S., Seeger, R. & Pople, J. A. Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J. Chem. Phys. 72, 650, (1980). b) McLean, A. D. & Chandler, G. S. Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18. J. Chem. Phys. 72, 5639, (1980). c) Clark, T., Chandrasekhar, J., Spitznagel, G. n. W. & Schleyer, P. V. R. Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F. J. Comp. Chem. 4, 294-301, (1983). d) Frisch, M. J., Pople, J. A. & Binkley, J. S. Self-consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets. The Journal of Chemical Physics 80, 3265, (1984).

15 a) Hratchian, H. P. & Schlegel, H. B. Accurate reaction paths using a Hessian based predictor–corrector integrator. J. Chem.

Phys. 120, 9918, (2004). b) 1 Hratchian, H. P. & Schlegel, H. B. Using Hessian Updating To Increase the Efficiency of a Hessian Based Predictor-Corrector Reaction Path Following Method. J. Chem. Theory Comput. 1, 61-69, 83 (2005).

16 Tomasi, J., Mennucci, B. & Cancès, E. The IEF version of the PCM solvation method: an overview of a new method addressed to study molecular solutes at the QM ab initio level. J. Mol. Struct. (Theochem) 464, 211-226, (1999).

17 A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B, 2009, 113, 6378.

18 Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.




82

The ωB97X-D functional was found to be a very promising DFT method in a recent benchmark study19 yielding reasonably accurate data for general main group thermochemistry, kinetics and noncovalent interactions (all relevant to our present work). It should be, however, taken into account that the mean absolute error of the wB97X-D method for predicting reaction energies is 2.5 kcal/mol. Considering the empirical ingredients of the polarizable continuum solvent model and the approximations employed in the calculation of gas-phase entropic contributions, the error bar on the relative Gibbs free energies reported in the present work is expected to be even larger (about 3-4 kcal/mol). All our conclusions in this paper were drawn in the light of these uncertainties.

Computational Results

Some mechanistic aspects of the reported alkyne hydrogenation reactions have been addressed computationally as well. Our primary goal was to explore the elementary steps of the proposed catalytic cycle (Figure 2b in the paper), however, we examined reaction pathways corresponding to the generation of catalyst 8 from aminoborane 6 (Figure 2a in the paper) as well as various side-reactions that may compete with the elementary steps of the catalytic cycle. Herein, we provide a detailed description of the obtained results.

Section S48. Generation of the catalyst

The reaction pathway investigated for the formation of aminohydroborane acting as a catalyst in the hydrogenation of alkynes is depicted in Scheme C1. For the simplicity of the discussion presented in the following sections, we introduce a new notation for the involved species. The datively bound forms of the precursor aminoborane and the catalyst hydroborane are denoted as pre and cat, respectively, whereas their “open” forms (i.e. those with unquenched active centers) will be referred to as pre' and cat'. As demonstrated previously,20 amoniborane pre reacts with dihydrogen to give ammonium borohydride preH2, which is assumed to undergo intramolecular protonation resulting in the elimination of C6F5H.

N

B

C6F5C6F5

N

B

H

H

C6F5 C6F5

N

BH

C6F5

N

B

C6F5

C6F5

N

B

C6F5H+ H2 - C6F5H

TS1 TS2

pre pre' preH2 cat' cat

Scheme C1. Formation of aminohydroborane cat.

We note first that the experimentally observed four-membered ring structure of the precursor aminoborane pre is well reproduced by the applied DFT method (see Figure C1). The computed B-N bond distance is 1.78 Å, which is reasonably close to those obtained from the X-ray structure (1.77 and 1.74 Å for the two molecules in the unit cell).8 The relative stability of the open form of the precursor is predicted to be almost identical to the datively bound structrure pointing to the strained nature of the four-membered ring in pre.

19 Goerigk, L. & Grimme, S. A thorough benchmark of density functional methods for general main group thermochemistry, kinetics,

and noncovalent interactions. Phys. Chem. Chem. Phys. 13, 6670, (2011).

20 Chernichenko, K., Nieger, M., Leskelä, M. & Repo, T. Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers’ ansa-aminoborane. Dalton Trans. 41, 9029-9032 (2012).




83

pre (0.0) pre’ (-0.3)

1.78 [1.77, 1.74]

2.99

Figure C1. The closed (pre) and open (pre') forms of the precursor aminoborane. Computed B-N bond distances are given in Å; experimental data are shown in brackets. Relative Gibbs free energies (in kcal/mol) are shown in parenthesis.

Due to the unquenched Lewis centers, pre' can act as a reactive species in the reaction with H2 yielding the ammonium borohydride preH2. The transition state (TS) located for the hydrogen activation process (TS1 in Figure C2) displays similar structural features as those described for other FLP + H2 reactions (early nature of the TS, end-on donor···H2 and side-on H2···acceptor interactions, etc.), and the predicted barrier indicates that the heterolytic cleavage of H2 is kinetically allowed. The formation of the zwitterionic preH2 species is computed to be only slightly exergonic, which is consistent with the observed reversibility of the hydrogen uptake by aminoborane pre.20

TS1 (16.3)

TS2 (18.7)

preH2 (-4.3)

pre’ + H2 (-0.3)

cat’ (a) + C6F5H (-1.1)

0.77

1.53

1.41

1.94

1.28

Figure C2. Optimized structures of stationary points identified along the reaction pathway from the precursor to the catalyst. Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to pre + H2) are shown in parenthesis.

The elimination of C6F5H takes place in a single step via transition state TS2, thus the internal proton transfer and the B−C cleavage are concerted processes. The activation barrier represented by TS2 is notably higher than that of the hydrogen activation step, which is in line with the fact




84

that the generation of the catalyst requires higher temperatures.21 The product side of the C6F5H elimination step correlates with an open form of the catalyst molecule (cat'(b) in Figure C3) lying only 1.1 kcal/mol below the reactants in free energy, however, the dative bond formation between the Lewis centers provides significant stabilization for the catalyst (see cat in Figure C3).22 The overall Gibbs free energy change of the pre + H2 → cat + C6F5H reaction is -7.3 kcal/mol. We note that another isomeric form of the open structure could be identified for the catalyst molecule (cat'(a) in Figure C3), which differs in the position of the hydride and C6F5 groups at the B atom, and it is predicted to be slightly more stable than the cat'(b) isomer.

cat’(b) (-1.1) cat (-7.3)cat’(a) (-1.8)

1.74

Figure C3. The open and closed forms of the catalyst molecule. The B-N bond length in cat is given in Å. Relative Gibbs free energies of catalyst + C6F5H states (in kcal/mol, with respect to pre + H2) are shown in parenthesis.

The computed energetics for the entire route from pre + H2 to cat + C6F5H is summarized in the form of Gibbs free energy profile (Figure C4). These results provide support for the mechanism proposed in the paper.

21 In principle, proton migration to the carbon of the bridging phenyl ring (carbon adjacent to the boron center) may result in the formation of N,N-dimethyl-N-phenylamine and B(C6F5)2H (Piers borane), but the estimated barrier (~45 kcal/mol) excludes the kinetic feasibility of this process. The high barrier can be associated with the unfavored geometry of the 1,3-proton migration. 22 The enhanced stability of the four-membered ring structure of the catalyst (as compared to the precursor) might be surprising in light of the reduced acidity implied by the C6F5H → H substitution, however, this could be rationalized by the reduced back-strain in the less bulky aminohydroborane.




85

Figure C4. Gibbs free energy profile of catalyst generation.

Section S49. Catalytic cycle for the hydrogenation of but-2-yne

The elementary steps of the envisioned catalytic cycle for the hydrogenation of internal alkynes (Figure 2b in the manuscript) were explored computationally using but-2-yne as a relevant model substrate. But-2-yne was hydrogenated experimentally as well and did not show any difference in reactivity in comparison to other internal alkynes. The key intermediates and transition states involved in the cycle are shown in Scheme C2.

TShydr

+

N

BC6F5

+ H2

TSsplitN

B

H

H

C6F5

−−−−

TSprot

cat cat'

intH2

cat' cat

int'

N

BC6F5

int

Scheme C2. Elementary steps of the catalytic cycle considered in the present computational study for but-2-yne hydrogenation.

We identified two different reaction pathways for the hydroboration of but-2-yne corresponding to the cat'(a) and cat'(b) open forms of the catalyst (Figure C4). Of the two transition states, TShydr(a) represents a lower activation barrier, which is partially due to the slight thermodynamic preference of cat'(a), but it is likely that steric hindrance between the hydride moiety and the amine methyl group in TShydr(b) destabilizes this latter transition state.




86

TShydr(a) (16.2)

1.70

TShydr(b) (18.0)

1.70

1.75

1.71

2.20

Figure C4. Transition states of the hydroboration of but-2-yne with cat'(a) and cat'(b). Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to cat + but-2-yne) are shown in parenthesis.

Interestingly, the IRC calculations following the minimum energy pathways towards the reactant states reveal shallow energy minima on the potential energy surface (PES), which correspond to adducts formed between the substrate and the borane unit of the catalyst. For the reaction with cat'(a), this adduct (see cat'(a)⋅⋅⋅but-2-yne in Figure C5) is predicted to lie only 0.9 kcal/mol below TShydr(a) in free energy. The adduct formation is found to occur via transition state TSadd(a), which is also very close to the adduct in free energy (separated only by 0.5 kcal/mol). Although the borane⋅⋅⋅but-2-yne adduct represents a well-defined minimum on the PES,23 the computed energetics (i.e. unfavored thermodynamics and low barriers on both sides) suggests that it cannot be regarded as an important reaction intermediate in the present catalytic cycle. For this reason, the adduct formation is not considered as a separate step in the paper.

TSadd(a) (15.8) cat’(a)⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅⋅but-2-yne (15.3)

2.35

2.35

1.99

1.92

Figure C5. Transition states of the addition of but-2-yne to cat'(a) and the high-lying adduct species. Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to cat + but-2-yne) are shown in parenthesis.

Given the appreciable difference in the relative free energies of the two hydroboration transition states (1.8 kcal/mol, see Figure C4), we only followed the kinetically more favored pathway. On the product side of TShydr(a), various isomers of alkenyl borane intermediates are feasible (see Figure C6).

23 The adduct species (cat'(b)⋅⋅⋅but-2-yne) and the corresponding transition state of its formation (TShydr(b)) could also be identified for the hydroboration with cat'(b), and the computed relative stabilities are identical within 0.1 kcal/mol (15.6 kcal/mol with respect to cat + but-2-yne).




87

int1’ (-23.1)int1 (-22.3)

int2’ (-22.8)int2 (-22.0)

1.85

1.85

Figure C6. Various isomeric forms of alkenyl borane intermediates formed in the hydroboration step. Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to cat + but-2-yne) are shown in parenthesis.

Transition state TShydr(a) correlates directly with isomer int1' and lies 23.1 kcal/mol below the reactants. The closed form of this species (int1) is predicted to be slightly less stable (only by 0.8 kcal/mol), which can be attributed to the reduced Lewis acidity and the increased bulkiness of the borane as compared to the catalyst molecule. Both effects contribute to the weakening of the dative bond, which is clearly reflected in the computed B−N bond lenghts. Isomerization of int1 via the rotation of the alkenyl group can easily occur (the computed barrier is 7.7 kcal/mol) leading to int2, and the ring opening yields int2'. The relative stabilities of all these isomers are predicted to be within a very narrow range (~1 kcal/mol) and they are interconnected by low barriers, therefore they are expected to be in equilibrium in solution.

The open forms of alkenyl borane species (int1' and int2') can be regarded as reactive intermediates in the hydrogen activation step of the catalytic cycle, as they are shown to cleave H2 heterolytically via relatively low activation barriers. For instance, the transition state located for the reaction of int2' with H2 (TSsplit in Figure C7) is computed to be at -7.3 kcal/mol relative to the cat + but-2-yne + H2 level, which corresponds to a barrier of 15.8 kcal/mol with respect to the most stable form of alkenyl borane intermediate (int1').

24 The computations thus show that the hydrogen splitting step of the cycle is kinetically allowed, however, in contrast to the analogous reaction with pre', the formation of the ammonium hydridoborate intermediate (intH2) is found to be endergonic (intH2 lies 2.7 kcal/mol above int1' + H2). The unfavored thermodynamics stems from the reduced acidity of the borane unit when replacing the electron withdrawing C6F5 unit by the butenyl group.

24 The barrier of H2 splitting is computed to be somewhat higher (18.2 kcal/mol) for the int1' + H2 pathway.




88

TSsplit (-7.3) intH2 (-20.4)

0.78 1.49

Figure C7. Transition state of H2 splitting in the reaction with int2' and the corresponding ammonium hydridoborate intermediate intH2. Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to cat + but-2-yne + H2) are shown in parenthesis.

The structure of the zwitterionic intermediate intH2 can easily rearrange by internal rotations around the B−C bonds, and in one of these structures (intH2

prot in Figure C8), the N−H bond of the protonated amine points towards the alpha carbon atom of the alkenyl group. A proton shift process in this arrangement is predicted to occur via a fairly low barrier (14.5 kcal/mol with respect to intH2

prot), and the analysis of the located transition state (TSprot in Figure C8) reveals a concerted B−C bond cleavage that leads to the elimination of cis-but-2-ene and the regenaration of the catalyst. This step is favored thermodynamically as well, since the product side (cat + cis-but-2-ene) is computed to be 10.4 kcal/mol more stable than the intH2 intermediate. The exergonicity of the overall hydrogenation reaction (but-2-yne + H2 → cis-but-2-ene) is -31.0 kcal/mol.25

1.98

1.46

1.79

1.27

TSprot (-5.6)intH2prot (-20.1)

Figure C8. Reaction intermediate on the reactant side of the internal protonation process (intH2prot) leading

to the elimination of cis-but-2-ene product, and the corresponding transition state (TSprot). Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to cat + but-2-yne + H2) are shown in parenthesis.

Proton migration to the carbon atom of the perflouoro aryl group in intermediate intH2 leading to the elimination of C6F5H is a possible competing protonation pathway, which has been 25 This value is well consisted with the one estimated from tabulated experimental data: ∆G° = ∆Gf°(cis-but-2-ene(g)) - ∆Gf°(but-2-yne(g)) - ∆Gf°(H2(g)) = 65.9 – 185.4 – 0 = -119.5 kJ/mol = 28.6 kcal/mol. Tabulated values for the compounds in a gas phase are available: Lange, N. A. Lange’s handbook of chemistry (New York : McGraw-Hill, 1973).




89

explored computationally. The calculations show that this side reaction is thermodynamically feasible (the prodAr-prot + C6F5H state is predicted to lie 3.7 kcal/mol below intH2 in free energy), however, based upon the computed barriers, the aryl elimination is notably less favored kinetically as compared to cis-but-2-ene formation (TSAr-prot represents a barrier of 19.1 kcal/mol relative to intH2). The selective cleavage of the B−C bond of the alkenyl borane unit in intH2 can be associated with the reduced electron density of the π system in the perfluoro aryl group.

1.32

2.03

1.34

TSAr-prot (-1.3) prodAr-prot (-24.1)

1.81

Figure C9. Transition state located for the protonation of the aryl group leading to the elimination of C6F5H (TSAr-prot), and the aminoborane formed on the product side (prodAr-prot). Selected bond distances are given in Å. Relative Gibbs free energies (in kcal/mol, with respect to cat + but-2-yne + H2) are shown in parenthesis.

The Gibbs free energy diagram derived for the examined catalytic cycle is depicted in Figure C10. The zero level used as a reference for the estimation of relative stabilities corresponds to cat + but-2-yne + H2. As noted previously, a number of different conformers can be identified for a given intermediate or transition state. For the sake of clarity, we show only the most stable species in this figure. Figure C3 presented in the manuscript was derived by further simplification, namely by omitting data corresponding to cat', TSadd and cat'⋅⋅⋅but-2-yne.

Figure C10. Gibbs free energy profile computed for the catalytic hydrogenation of but-2-yne. The notation of reaction intermediates and transition states corresponds to that introduced in Scheme C2 and further in the text




90

(herein, reactant but-2-yne and product cis-but-2-ene are denoted as but and cis-butH2). Energy data (in kcal/mol) for various states along the reaction pathway are shown in parentheses. δE (given in kcal/mol) refers to the energetic span of the catalytic cycle.

The free energy profile demonstrates that all elementary steps of the reaction mechanism proposed in our paper, namely the alkyne hydroboration, hydrogen activation, and intramolecular protonation, can be identified computationally, and these steps are found to be kinetically and thermodynamically feasible. In addition to these basic reaction steps, the importance of the open forms of the catalyst and the alkenyl borane intermediate should be mentioned, as they represent the reactive forms of these species. Adduct formation between the borane unit of the catalyst and the alkyne substrate prior to the hydroboration steps could also be identified in our calculations, however, the intermediacy of the adduct species cannot be clearly established from the present results.

Of the located transition states, TShydr is predicted to be the highest lying in terms of Gibbs free energies. However, the computed energetics suggest that the hydroboration step does not necessarily represent the rate-determining process of the catalytic cycle. Following the terminology of the recently formulated energetic span model,26 the kinetics of the cycle is controlled by the energy difference between the TOF-determining transition state (TDTS) and the TOF-determining intermediate (TDI). In our particular case, the two states that define the energetic span of the cycle are TSprot and int' as illustrated in Figure C10. The computed energetic span is δE = 18.4 kcal/mol, which is clearly larger than the barrier represented by the transition state of hydroboration (16.2 kcal/mol).

Section S50. Catalytic cycle for the hydrogenation of cis-but-2-ene

To provide insight into the limiting factors in the hydrogenation of alkenes, reaction pathways for the cat + cis-but-2-ene + H2 system were explored computationally. We considered a catalytic cycle analogous to the reaction discussed in the previous section, and identified the intermediates and transition states relevant to the elementary steps of the cycle (see Scheme C3). The free energy profiles obtained for the reactions with the two substrates are shown in Figure C11. Herein, we do not intend to give a detailed description of the structure and energetics of all involved species, but we rather wish to focus on the main differences between the two systems, as well as their origin. The structural information (Cartesian coordinates) of all investigated intermediates and transition states are provided in Section S53.

26 For the basic concepts of this model and related applications, see: a) Kozuch, S. & Shaik, S. How to Conceptualize Catalytic

Cycles? The Energetic Span Model. Acc. Chem. Res. 44, 101-110, (2011). b) Kozuch, S. A refinement of everyday thinking: the energetic span model for kinetic assessment of catalytic cycles. Comput. Mol. Sci. 2, 795-815, (2012).




91

TShydr

+

N

BC6F5

+ H2

TSsplitN

B

H

H

C6F5

−−−−

TSprot

cat cat'

intH2

cat' cat

int'

N

BC6F5

int

Scheme C3. Elementary steps of the catalytic cycle considered in the present computational study for but-2-ene hydrogenation.

Figure C11. Gibbs free energy profiles computed for the catalytic hydrogenation of but-2-ene (in red) and but-2-yne (in blue). The notation of reaction intermediates and transition states corresponds to that introduced in Scheme C3 (reactant cis-but-2-ene is denoted as cis-butH2). Energy data (in kcal/mol) for selected structures along the reaction pathway for cat + cis-but-2-ene + H2 are shown in parentheses. δE (given in kcal/mol) refers to the energetic span of the catalytic cycle.

The comparison of free energy diagrams shown in Figure C11 reveals two major differences in the energetics of the investigated catalytic cycles:

1) Although the kinetics of the hydroboration steps in the two reactions are quite similar, the intermediates formed in these processes (alkenyl boranes int/int' and alkyl boranes int/int') are predicted to have significantly different relative stabilities.27 Due to the reduced exergonicity of the cis-but-2-ene hydroboration, the remaining part of the cat + cis-but-2-ene + H2 diagram is shifted upwards with respect to the cat + but-2-yne + H2 profile. The reduced exergonicity of this

27 For alkyl borane intermediates, the closed forms become ~2 kcal/mol more stable with respect to their open isomers.




92

step also implies that the reversibility of hydroboration might be feasible at higher temperatures, which is in line with our observations.

2) The protonation step of the cis-but-2-ene cycle is found to be markedly less favored from kinetic point of view as expected from the sp3 hybridization of the proton acceptor carbon atom in the zwitterionic intH2 intermediate. As a results of high protonation barrier, the energetic span of this cycle is computed to be considerably larger relative to that of the but-2-yne cycle (28.8 versus 18.4 kcal/mol; see Figures C10 and C11). These results indicate that the intramolecular protonation step represents the main limiting factor towards the hydrogenation of internal alkenes using the present type of catalysts.

Section S51. Catalytic cycle for the hydrogenation of ethylene

Ethylene represents the simplest model substrate to examine possible hydrogenation pathways of terminal alkenes computationally. We have therefore considered the cat + ethylene + H2 system and derived a Gibbs free energy profile assuming elementary step similar to those presented above (see Scheme C4). The results are summarized in Figure C12.

TShydr

+

N

BC6F5

+ H2

TSsplitN

B

H

H

C6F5

−−−−

TSprot

cat cat'

intH2

cat' cat

int'

N

BC6F5

int

C2H6C2H4

Scheme C4. Elementary steps of the catalytic cycle considered for ethylene hydrogenation.

In contrast to previously described reactions, no borane⋅⋅⋅ethylene adduct species could be identified in the present case. The hydroboration thus takes place in a single step, and the computed barrier is comparable to those obtained for the other two reactions. The exergonicity of hydroboration is significantly larger than that of the cat + cis-but-2-ene reaction, which explains the irreversibility and related catalyst deactivation observed for terminal alkenes (see main text). The remaining part of the free energy profile is similar to that computed for the cis-but-2-ene cycle, i.e. it indicates facile H2 splitting process (with the equilibrium shifted to the int + H2 reactant state), and kinetically hindered internal protonation with an energetic span practically identical to that of the cis-but-2-ene cycle.




93

Figure C12. Gibbs free energy profiles computed for the catalytic hydrogenation of ethylene. The notation of reaction intermediates and transition states corresponds to that introduced in Scheme C4. Energy data (in kcal/mol) for for intermediates and transition states along the reaction pathway are shown in parentheses. δE (given in kcal/mol) refers to the energetic span of the catalytic cycle.

Section S52. Total energy data of the calculated structures

The energy data computed for the ωB97XD/6-311G(d,p) optimized geometries of the structures discussed in the manuscript and in the Supplementary Information are listed in Table C1. The notation of the structures is defined throughout the text of the Supporting Information (species identified for the catalytic cycles of cis-but-2-ene and ethylene are marked in red and green; see also Schemes C3 and C4). Table C1: Energy data (in atomic units) computed for ωB97XD/6-311G(d,p) optimized structures.a

structures Eo Go Gsol Eo′ G

H2 -1.1761 -1.1775 -1.1757 -1.1766 -1.1746 but-2-yne -155.9613 -155.9053 -155.9676 -155.9745 -155.9219

cis-but-2-ene -157.2114 -157.1309 -157.2163 -157.2245 -157.1458 butane -158.4491 -158.3443 -158.4538 -158.4612 -158.3581 ethene -78.5795 -78.5505 -78.5810 -78.5869 -78.5564 ethane -79.8248 -79.7730 -79.8272 -79.8312 -79.7787

pre -1846.0248 -1845.8108 -1846.0380 -1846.1870 -1845.9832 pre' -1846.0197 -1845.8094 -1846.0313 -1846.1855 -1845.9837 TS1 -1847.1846 -1846.9587 -1847.1960 -1847.3494 -1847.1318

preH2 -1847.2195 -1846.9844 -1847.2384 -1847.3838 -1847.1646 TS2 -1847.1826 -1846.9536 -1847.1958 -1847.3469 -1847.1280

cat'(a) -1118.8175 -1118.6367 -1118.8278 -1118.9164 -1118.7429 cat'(b) -1118.8150 -1118.6344 -1118.8259 -1118.9145 -1118.7418




94

cat -1118.8294 -1118.6451 -1118.8417 -1118.9268 -1118.7517 C6F5H -728.3740 -728.3473 -728.3772 -728.4442 -728.4176

TSadd(a) -1274.7878 -1274.5270 -1274.8018 -1274.8982 -1274.6484 cat'(a)⋅⋅⋅but-2-yne -1274.7893 -1274.5271 -1274.8041 -1274.8996 -1274.6492

TShydr(a) -1274.7873 -1274.5253 -1274.8022 -1274.8978 -1274.6478 TSadd(b) -1274.7874 -1274.5272 -1274.8011 -1274.8983 -1274.6488

cat'(b)⋅⋅⋅but-2-yne -1274.7874 -1274.5271 -1274.8012 -1274.8982 -1274.6487 TShydr(b) -1274.7854 -1274.5239 -1274.7995 -1274.8955 -1274.6450

int1' -1274.8546 -1274.5899 -1274.8681 -1274.9645 -1274.7104 int1 -1274.8574 -1274.5907 -1274.8713 -1274.9650 -1274.7091 int2' -1274.8531 -1274.5888 -1274.8668 -1274.9634 -1274.7099 int2 -1274.8559 -1274.5894 -1274.8701 -1274.9639 -1274.7086

TSsplit -1276.0183 -1275.7399 -1276.0316 -1276.1278 -1275.8597 intH2 -1276.0402 -1275.7539 -1276.0606 -1276.1497 -1275.8807

intH2prot

-1276.0407 -1275.7531 -1276.0609 -1276.1505 -1275.8802 TSprot -1276.0178 -1275.7359 -1276.0333 -1276.1265 -1275.8570

TSAr-prot -1276.0104 -1275.7295 -1276.0256 -1276.1190 -1275.8503 prodAr-prot -547.6510 -547.4154 -547.6651 -547.6935 -547.4689

TSadd -1276.0366 -1275.7488 -1276.0511 -1276.1463 -1275.8701 cat'(a)⋅⋅⋅but-2-ene -1276.0368 -1275.7491 -1276.0516 -1276.1464 -1275.8706

TShydr -1276.0360 -1275.7484 -1276.0510 -1276.1454 -1275.8697 int' -1276.0826 -1275.7936 -1276.0960 -1276.1918 -1275.9133 int -1276.0898 -1275.7981 -1276.1040 -1276.1969 -1275.9165

TSsplit -1277.2496 -1276.9467 -1277.2628 -1277.3582 -1277.0653 intH2 -1277.2748 -1276.9627 -1277.2946 -1277.3830 -1277.0876 TSprot -1277.2306 -1276.9237 -1277.2463 -1277.3395 -1277.0452 TShydr -1197.3961 -1197.1656 -1197.4086 -1197.5008 -1197.2798

int' -1197.4568 -1197.2236 -1197.4688 -1197.5606 -1197.3365 int -1197.4665 -1197.2286 -1197.4798 -1197.5685 -1197.3408

TSsplit -1198.6249 -1198.3753 -1198.6368 -1198.7281 -1198.4875 intH2 -1198.6488 -1198.3905 -1198.6676 -1198.7516 -1198.5091 TSprot -1198.6061 -1198.3542 -1198.6205 -1198.7099 -1198.4695

a Notation: Eo and Eo′ refer to electronic energies computed at ωB97XD/6-311G(d,p) and ωB97XD/6-311++G(3df,3pd) level of DFT; Go and Gsol denote gas-phase and solution-phase Gibbs free energies obtained from ωB97XD/6-311G(d,p) calculations. The last column is obtained as G = Eo′ + (Go - Eo) + (Gsol - Eo) + 0.00302 and the relative energies discussed in the manuscript and in the SI are obtained from these values. The value 0.00302 a.u. corresponds to concentration correction to the free energy when switching from p = 1 atm (ideal gas standard state) to c = 1mol/dm3 (standard concentration in solution phase).

Section S53. Cartesian coordinates of the calculated structures

Cartesian coordinates of ωB97XD/6-311G(d,p) optimized geometries are given below in standard XYZ format (units are in Å). First line indicates total number of atoms, second line is molecule name (as defined above, see also Table C1). 2 H2 -0.372198 0.000000 0.000000 0.372198 0.000000 0.000000 10 but-2-yne C 2.059149 -0.000087 -0.000040 C 0.600085 0.000929 0.000533 C -0.600085 0.000929 0.000533 C -2.059149 -0.000087 -0.000040 H 2.449567 0.790069 -0.646374 H 2.449846 0.164023 1.007409 H 2.448483 -0.955169 -0.361659




95

H -2.449567 0.790069 -0.646374 H -2.449846 0.164023 1.007409 H -2.448483 -0.955169 -0.361659 12 cis-but-2-ene C 2.095792 -1.815362 -3.044437 C 0.790420 -1.891434 -2.310431 C -0.243609 -2.688953 -2.567133 C -0.365459 -3.713457 -3.655136 H 0.694892 -1.205909 -1.470865 H -1.113873 -2.600813 -1.919947 H 2.156954 -2.514562 -3.879295 H 2.256384 -0.806761 -3.438866 H 2.929936 -2.026870 -2.367636 H -1.219258 -3.487066 -4.302014 H 0.523513 -3.775331 -4.284091 H -0.545565 -4.705983 -3.229609 14 butane C 1.925164 1.963607 -3.687063 C 1.600924 0.481720 -3.867829 C 1.298369 0.083520 -5.315008 C 2.477346 0.267987 -6.268707 H 0.738097 0.225425 -3.243853 H 2.437747 -0.122854 -3.497320 H 0.442424 0.666963 -5.675612 H 0.983643 -0.965367 -5.333703 H 2.841159 2.245043 -4.213162 H 1.114173 2.589910 -4.072576 H 2.064487 2.210522 -2.631570 H 2.233909 -0.094397 -7.270634 H 2.763440 1.319034 -6.360890 H 3.353787 -0.285760 -5.916832 6 ethene C 2.712094 -2.288993 0.954916 C 1.539619 -2.900517 0.883271 H 3.156598 -1.808018 0.089712 H 0.976600 -2.944207 -0.043295 H 1.094808 -3.381304 1.748373 H 3.275227 -2.245063 1.881349 8 ethane C 2.246091 1.084749 3.902122 C 2.652010 0.283767 5.135996 H 1.213692 0.871721 3.612789 H 2.884547 0.847269 3.047162 H 2.323291 2.159850 4.083928 H 3.684265 0.497168 5.425569 H 2.013139 0.520814 5.990740 H 2.575250 -0.791355 4.953970 42 pre C 5.592677 6.848691 5.677826 C 4.354986 6.566348 5.103873 C 4.190326 7.062379 3.816165 C 5.148329 7.822395 3.160216 C 6.351456 8.095278 3.785305




96

C 6.579329 7.596179 5.056399 B 3.347589 5.621207 5.962293 C 3.582952 4.051534 5.620964 C 3.265692 3.490097 4.389270 C 3.502145 2.166758 4.060315 C 4.110332 1.339526 4.990377 C 4.464281 1.853146 6.225112 C 4.199253 3.184415 6.517715 F 2.679101 4.242602 3.445454 F 3.155608 1.686671 2.868900 F 4.352286 0.068187 4.697882 F 5.057357 1.069292 7.120899 F 4.591099 3.603448 7.722965 F 3.067668 6.830310 3.120276 F 4.918827 8.284520 1.933725 F 7.279505 8.817657 3.170586 F 7.738753 7.831172 5.663569 F 5.897395 6.359578 6.886410 C 3.108352 6.012096 7.509426 C 3.621790 6.157788 8.793893 C 2.754733 6.561350 9.804869 C 1.401965 6.813950 9.558433 C 0.871766 6.677033 8.279620 C 1.776941 6.279519 7.312570 N 1.619630 6.057173 5.872528 C 0.651423 4.982399 5.570181 C 1.215100 7.307739 5.193437 H 4.662498 5.958394 9.012190 H 3.132691 6.680611 10.814276 H 0.758944 7.122103 10.374738 H -0.174476 6.873498 8.074470 H 0.258950 7.644485 5.602399 H 1.119936 7.131264 4.126499 H 1.970176 8.071412 5.375655 H 0.933168 4.083683 6.116195 H 0.660209 4.782158 4.500539 H -0.349564 5.293744 5.880043 42 pre'

C -1.002529 -0.856147 2.067618 C 0.021686 -0.082252 1.459319 C -0.050940 0.140808 0.072673 C -1.021262 -0.447662 -0.718381 C -1.965499 -1.269703 -0.113911 C -1.967315 -1.467311 1.258135 B 1.332697 0.308470 2.155595 C 2.189300 1.515165 1.601432 C 3.519968 1.362772 1.236243 C 4.289139 2.414411 0.767088 C 3.721087 3.676204 0.675077 C 2.398019 3.871985 1.042134 C 1.655776 2.792624 1.491413 F 4.091793 0.156960 1.307751 F 0.391356 3.020405 1.858332 F 1.862443 5.085112 0.962669 F 4.443432 4.696384 0.235341 F 5.554531 2.230355 0.407325 N -1.022999 -1.008631 3.449743 C -0.975610 0.165098 4.306341 C -1.774244 -2.101662 4.025855 H -0.328575 -0.013388 5.171116 H -1.432472 -2.253997 5.052575




97

H -2.859365 -1.914171 4.056277 H -1.586290 -3.021470 3.470385 H -0.593409 1.026861 3.761121 H -1.980909 0.418656 4.672743 H -2.746315 -2.073573 1.701803 H -2.732612 -1.745462 -0.715485 H -1.037501 -0.281185 -1.788301 H 0.712289 0.752093 -0.397449 C 1.939626 -0.486941 3.377379 C 1.977751 -1.876780 3.424854 C 2.511944 -2.568985 4.496680 C 3.030481 -1.864137 5.573839 C 3.009766 -0.479562 5.567459 C 2.474886 0.179739 4.472133 F 1.496369 -2.598419 2.413596 F 2.533700 -3.898304 4.507506 F 3.540113 -2.516748 6.608762 F 3.492488 0.197854 6.604199 F 2.440947 1.516952 4.521245 44 TS1

C -0.046584 0.133872 -0.094613 C -0.021715 -0.005699 1.297125 C -1.198317 -0.422046 1.935071 C -2.347502 -0.687455 1.195874 C -2.340613 -0.564182 -0.186143 C -1.183813 -0.153822 -0.834877 B 1.330411 0.288131 2.057459 C 2.104191 -0.864879 2.837777 C 2.037950 -2.199751 2.460111 C 2.719780 -3.203300 3.131369 C 3.510948 -2.878515 4.220123 C 3.614896 -1.556335 4.624590 C 2.924713 -0.583122 3.924936 F 1.295668 -2.577029 1.416128 F 2.615158 -4.470184 2.742974 F 4.166419 -3.826778 4.874107 F 4.375397 -1.239898 5.667253 F 3.061536 0.681093 4.342346 N -1.195511 -0.538257 3.369749 C -2.234541 0.246455 4.024838 H -2.050214 0.250344 5.102422 C 2.177155 1.531756 1.527552 C 1.609829 2.797587 1.410147 C 2.298137 3.887518 0.906189 C 3.606122 3.721517 0.477305 C 4.206056 2.476078 0.562372 C 3.489983 1.410661 1.086046 F 0.355382 3.005186 1.819379 F 4.113151 0.229256 1.125074 F 5.455268 2.313246 0.140327 F 4.278555 4.751092 -0.016086 F 1.722310 5.082307 0.827908 C -1.184790 -1.922006 3.831308 H -0.936670 -1.950137 4.895648 H -2.158579 -2.416917 3.687164 H -0.435066 -2.488925 3.281368 H -2.196615 1.275722 3.662805 H -3.248806 -0.146760 3.855833 H -3.253202 -1.000431 1.704356 H -3.237690 -0.784255 -0.753674 H -1.170696 -0.047775 -1.913441




98

H 0.846966 0.469329 -0.611541 H 0.321719 0.713711 3.580375 H 0.864700 1.263596 3.530390 44 preH2 C -1.397616 1.897299 1.294690 C -1.068947 1.107713 0.185660 C -1.480705 1.619574 -1.039386 C -2.167925 2.813370 -1.210260 C -2.467021 3.564099 -0.085331 C -2.079227 3.097901 1.167897 B -0.223434 -0.289128 0.277649 C 1.349584 0.091876 0.049704 C 2.069879 0.856687 0.959181 C 3.382833 1.246813 0.761021 C 4.029946 0.884986 -0.411421 C 3.350910 0.140591 -1.358772 C 2.039844 -0.237205 -1.105750 F 1.491538 1.243281 2.103146 F 4.029071 1.969466 1.672549 F 5.287533 1.259315 -0.626476 F 3.951701 -0.196629 -2.500770 F 1.428547 -0.934759 -2.095134 N -1.155310 0.795879 -2.225852 C -2.363533 0.268466 -2.909392 H -2.051902 -0.415274 -3.698960 C -0.604150 -1.139040 1.608898 C -1.947252 -1.410662 1.851370 C -2.404303 -2.140857 2.934615 C -1.486567 -2.654563 3.836381 C -0.137330 -2.433495 3.627475 C 0.276628 -1.696539 2.525265 F -2.882802 -0.965417 0.992169 F 1.601872 -1.559668 2.380370 F 0.753714 -2.936416 4.480845 F -1.899428 -3.360121 4.886030 F -3.707096 -2.361437 3.113554 C -0.194368 1.448741 -3.149571 H 0.133177 0.722325 -3.891837 H -0.680249 2.296450 -3.631221 H 0.656756 1.791849 -2.564383 H -2.962860 -0.256539 -2.167141 H -2.932609 1.095754 -3.330642 H -2.467036 3.160344 -2.194070 H -2.999395 4.502177 -0.185079 H -2.313728 3.679189 2.052467 H -1.106461 1.552111 2.280027 H -0.691205 -0.031853 -1.796614 H -0.554417 -1.029076 -0.649072 44 TS2

C -0.028051 -0.210961 -0.012555 C -0.151931 -0.119632 1.376245 C -1.181186 -0.866644 1.964393 C -2.026065 -1.682305 1.223254 C -1.875981 -1.745367 -0.155060 C -0.877730 -1.002751 -0.772664 B 0.770221 0.826352 2.262354 C 1.280961 -0.195363 3.833837 C 2.040099 -1.340438 3.584492 C 3.291477 -1.544041 4.131792




99

C 3.789264 -0.595894 5.016116 C 3.036374 0.520923 5.362044 C 1.790225 0.685477 4.791058 F 1.550943 -2.285003 2.785670 F 4.009386 -2.623878 3.848988 F 4.980492 -0.771550 5.559397 F 3.522764 1.393743 6.237462 F 1.084669 1.753411 5.148360 N -1.298239 -0.769822 3.406559 C -2.199092 0.304007 3.847681 H -2.054392 0.476567 4.916671 C 2.164059 1.357233 1.669138 C 2.489399 2.709270 1.745118 C 3.683075 3.228152 1.265050 C 4.611286 2.379071 0.685972 C 4.334534 1.024957 0.591909 C 3.128663 0.547610 1.078908 F 1.642616 3.583408 2.294489 F 2.920978 -0.771431 0.970129 F 5.223547 0.202442 0.040702 F 5.759357 2.859101 0.224060 F 3.946274 4.529279 1.355659 C -1.554756 -2.031508 4.102985 H -1.371725 -1.882394 5.169681 H -2.586775 -2.373327 3.972982 H -0.870954 -2.791597 3.726158 H -1.958859 1.217526 3.307595 H -3.244213 0.033176 3.660292 H -2.803545 -2.260837 1.709376 H -2.537712 -2.371231 -0.742470 H -0.755371 -1.049146 -1.848816 H 0.754442 0.351933 -0.510431 H 0.021254 -0.391480 3.717568 H 0.162996 1.692965 2.818905 32 cat' (a)

C 2.354586 1.094038 4.546848 C 1.392169 1.116712 3.498857 C 0.473895 2.183024 3.465900 C 0.546273 3.249579 4.344635 C 1.552401 3.250510 5.304310 C 2.438794 2.189839 5.415020 B 1.410775 0.236616 2.246114 C 2.641897 -0.607687 1.740084 C 2.442608 -1.899799 1.271281 C 3.478446 -2.715328 0.842711 C 4.772065 -2.220569 0.859823 C 5.013483 -0.928610 1.305981 C 3.954345 -0.146024 1.731514 F 1.209924 -2.417749 1.269713 F 3.246252 -3.955152 0.421718 F 5.780200 -2.979431 0.451062 F 6.257772 -0.457264 1.316013 F 4.239303 1.093473 2.131871 N 3.210270 0.007493 4.685967 C 2.674252 -1.340277 4.756502 H 0.437264 0.220597 1.552315 C 4.443190 0.168104 5.423343 H -0.285895 2.179779 2.690979 H -0.158043 4.069875 4.281195 H 1.633140 4.077490 6.001952 H 3.176791 2.202351 6.206685




100

H 2.648851 -1.693787 5.797707 H 3.289651 -2.033371 4.172992 H 1.658805 -1.372418 4.365842 H 4.923477 1.109057 5.152854 H 5.120484 -0.643990 5.146416 H 4.304389 0.134277 6.515809 32 cat' (b)

C 3.495864 1.568532 1.486294 C 2.106900 1.650489 1.536116 C 1.550487 2.877336 1.183352 C 2.320499 3.961797 0.794719 C 3.699633 3.829509 0.741977 C 4.295885 2.625689 1.086391 B 1.252393 0.426281 2.033576 C -0.044457 -0.025615 1.356927 C -0.195124 0.183861 -0.024989 C -1.158095 -0.471543 -0.769832 C -2.017336 -1.351837 -0.118847 C -1.940402 -1.549649 1.249853 C -0.976886 -0.873562 2.015142 N -0.919965 -1.025111 3.391761 C -1.656650 -2.099733 4.019580 F 0.229643 3.061099 1.241480 F 1.755948 5.122487 0.476261 F 4.448903 4.854920 0.363566 F 5.618295 2.503922 1.032127 F 4.103268 0.426421 1.810595 C -0.755989 0.134127 4.255751 H 0.040651 -0.024464 4.988089 H -1.273694 -2.238895 5.032775 H -2.737138 -1.896203 4.089909 H -1.507307 -3.034034 3.476605 H -0.514364 1.018725 3.666880 H -1.691056 0.341126 4.795704 H -2.657144 -2.206334 1.725182 H -2.779937 -1.878258 -0.683126 H -1.236790 -0.311499 -1.838057 H 0.503415 0.843975 -0.529354 H 1.694264 -0.199849 2.948227 32 cat

C 0.478215 0.546711 0.247224 C 0.045907 0.119494 1.495238 C -1.186778 0.610176 1.900605 C -1.944657 1.475770 1.122723 C -1.466024 1.880418 -0.111862 C -0.238519 1.414017 -0.557772 B 0.927851 -0.924061 2.339633 C 0.791654 -1.085802 3.931689 C 0.062047 -1.501266 5.037952 C 0.667690 -1.422610 6.291171 C 1.970176 -0.942677 6.451562 C 2.716827 -0.516926 5.354646 C 2.069609 -0.612483 4.138242 N 2.484913 -0.270848 2.773320 C 3.635267 -1.046784 2.278027 F -1.709656 0.251425 3.078217 F -3.124150 1.920092 1.550568 F -2.176540 2.712815 -0.865053 F 0.230747 1.803655 -1.741337




101

F 1.668398 0.121891 -0.218837 C 2.699421 1.175733 2.588195 H 2.864025 1.380407 1.530467 H 3.722610 -0.891008 1.202704 H 4.554461 -0.727343 2.777963 H 3.457148 -2.102368 2.475567 H 1.816367 1.712959 2.931286 H 3.569705 1.501741 3.164471 H 3.726808 -0.138457 5.466123 H 2.403542 -0.897914 7.444075 H 0.117571 -1.739812 7.170545 H -0.952664 -1.870750 4.944434 H 1.148194 -1.936196 1.722231 12 C6F5H C 3.514674 -0.363605 3.376647 C 2.452251 -1.243875 3.293415 C 2.480001 -2.233180 2.328382 C 3.548677 -2.351706 1.453016 C 4.606653 -1.459093 1.551244 C 4.595862 -0.459739 2.513808 F 1.470259 -3.094503 2.226108 F 3.569821 -3.303897 0.528121 F 5.633756 -1.561884 0.720084 F 5.613073 0.389026 2.598771 F 3.513696 0.598604 4.296570 H 1.614125 -1.159871 3.971649 42 TSadd(a)

C -0.018637 -0.014870 0.006901 C -0.015736 -0.005775 1.403622 C -0.950884 0.831640 2.050123 C -1.776864 1.669692 1.299426 C -1.715874 1.674395 -0.087612 C -0.845105 0.816467 -0.740297 B 0.945420 -0.934703 2.259287 C 1.726057 -0.431540 3.555146 C 1.975493 0.902674 3.866916 C 2.578632 1.301810 5.046897 C 2.978690 0.344535 5.966618 C 2.770992 -0.995845 5.692638 C 2.158092 -1.355026 4.501535 F 1.641734 1.878888 3.018669 F 1.988745 -2.667791 4.296377 F 3.160361 -1.920437 6.567949 F 3.565040 0.712620 7.099236 F 2.783882 2.592148 5.305799 N -1.016640 0.812885 3.466705 C -1.481269 2.011613 4.127645 C -1.566388 -0.393863 4.058448 C 2.870826 -0.820877 0.916835 C 3.321399 0.557779 0.769579 C 2.584911 -1.995055 0.950065 C 2.351550 -3.434259 0.924187 H -1.205156 1.958049 5.184853 H -1.273260 -0.451714 5.111254 H -2.667649 -0.420885 4.001731 H -1.183181 -1.281909 3.554502 H -0.992910 2.885788 3.694654 H -2.574958 2.152199 4.076660 H -2.483113 2.320064 1.801494




102

H -2.363069 2.336163 -0.652702 H -0.800670 0.796148 -1.823351 H 0.671619 -0.667459 -0.517077 H 0.635942 -2.087060 2.314032 H 1.381491 -3.656711 0.475174 H 3.132569 -3.923951 0.338574 H 2.362443 -3.835626 1.938718 H 4.040673 0.621777 -0.049378 H 2.475495 1.213066 0.553399 H 3.803744 0.904955 1.685407 42 cat'(a)⋅⋅⋅but-2-yne C -1.716361 0.372852 1.584474 C -0.328129 0.264856 1.477426 C 0.171543 -0.641857 0.516181 C -0.706735 -1.428246 -0.231085 C -2.081691 -1.320310 -0.070361 C -2.592338 -0.402560 0.832004 B 0.662352 1.159970 2.375880 C 2.054617 0.568277 2.944375 C 2.283972 -0.774972 3.217919 C 3.518782 -1.269291 3.601340 C 4.584748 -0.396437 3.755831 C 4.397680 0.954576 3.523356 C 3.146122 1.405249 3.129786 F 1.293631 -1.669749 3.113700 F 3.028886 2.726527 2.915434 F 5.413266 1.802984 3.678438 F 5.774225 -0.853757 4.134118 F 3.692370 -2.571210 3.827441 N 1.575575 -0.762384 0.343260 C 2.087329 -2.045319 -0.081399 C 2.225313 0.345986 -0.329842 C -0.268042 1.360383 4.037282 C -0.551537 0.158658 4.822369 C -0.180047 2.490600 3.587133 C -0.192711 3.911102 3.251076 H 3.161987 -2.078784 0.123252 H 3.300483 0.319159 -0.125001 H 2.079219 0.313431 -1.423012 H 1.837028 1.296728 0.034821 H 1.609553 -2.841690 0.491207 H 1.948695 -2.248354 -1.157853 H -0.311557 -2.130266 -0.955995 H -2.745311 -1.942844 -0.660408 H -3.663447 -0.293815 0.961413 H -2.139998 1.072257 2.299020 H 0.904891 2.199788 1.817215 H -0.715984 4.073231 2.307293 H -0.705730 4.459327 4.044216 H 0.828924 4.281509 3.157150 H -1.237344 0.407428 5.633645 H -0.997755 -0.606498 4.185783 H 0.372760 -0.239588 5.244530 42 TShydr(a)

C 0.002438 -0.002901 0.000772 C 0.001662 -0.001850 1.397193 C -1.073915 0.647496 2.039137 C -2.048401 1.303387 1.283967 C -1.999063 1.307825 -0.103391




103

C -0.975947 0.636428 -0.752425 B 1.213920 -0.685856 2.212667 C 1.640109 -0.196443 3.690273 C 1.760701 1.148499 4.009717 C 2.066669 1.597924 5.281753 C 2.294226 0.674853 6.292103 C 2.207202 -0.677729 6.013534 C 1.886523 -1.081931 4.725637 F 1.554831 2.079206 3.068706 F 1.798305 -2.408884 4.513600 F 2.426903 -1.571451 6.977178 F 2.599775 1.088500 7.518635 F 2.147196 2.901352 5.546972 N -1.138229 0.645363 3.457098 C -1.769181 1.775289 4.099583 C -1.508935 -0.619243 4.061945 C 2.634225 -0.648186 1.275389 C 3.389454 0.539831 0.851566 C 2.363449 -1.859028 1.367483 C 2.422705 -3.318910 1.221637 H -1.478746 1.785734 5.154761 H -1.221977 -0.619481 5.118516 H -2.593458 -0.811596 3.996031 H -0.990558 -1.444096 3.572566 H -1.418598 2.702514 3.643523 H -2.872541 1.754834 4.059838 H -2.863682 1.810356 1.786811 H -2.766489 1.824167 -0.669549 H -0.927695 0.619512 -1.835546 H 0.808877 -0.504421 -0.527026 H 0.951634 -1.889258 2.320846 H 1.534655 -3.693384 0.708756 H 3.306644 -3.572319 0.632410 H 2.494735 -3.796508 2.200242 H 4.210199 0.275178 0.183906 H 2.714868 1.236735 0.350159 H 3.789369 1.048494 1.731645 42 TSadd(b)

C -0.974905 -0.221889 1.029449 C 0.331382 -0.548182 0.686142 C 0.504858 -1.014973 -0.612962 C -0.538695 -1.153715 -1.516255 C -1.824013 -0.819826 -1.123934 C -2.046187 -0.349708 0.160266 B 1.607472 -0.435867 1.654142 C 2.052482 0.992060 2.186985 C 1.300950 2.130029 1.883083 C 1.617548 3.389354 2.380414 C 2.715910 3.531796 3.211922 C 3.503795 2.426376 3.511999 C 3.195215 1.166081 3.001416 N 3.997804 0.031962 3.316822 C 4.659475 0.045529 4.604964 F 1.722657 -1.354702 -1.050528 F -0.319653 -1.604436 -2.749102 F -2.837080 -0.946975 -1.972877 F -3.279088 -0.025237 0.542831 F -1.255603 0.243384 2.255537 C 4.921458 -0.343896 2.255187 C 0.892208 -1.074784 3.719267 C 1.097987 -2.044145 3.024098




104

H 5.298520 -1.354813 2.436508 H 5.010292 -0.965431 4.829895 H 5.535201 0.716720 4.651031 H 3.958049 0.342586 5.387380 H 4.416292 -0.335042 1.291169 H 5.783391 0.343206 2.201478 H 4.374275 2.553776 4.144868 H 2.974438 4.503151 3.619374 H 1.003050 4.245869 2.127782 H 0.428146 2.031231 1.246993 H 2.480687 -1.184559 1.346799 C 0.617264 -0.014884 4.678973 C 1.282696 -3.321371 2.343926 H 0.773653 -3.316607 1.377586 H 2.344453 -3.506415 2.171053 H 0.871754 -4.128084 2.953942 H 0.018008 -0.418842 5.497845 H 1.550283 0.385849 5.078443 H 0.069570 0.799318 4.204621 42 cat'(b)⋅⋅⋅but-2-yne C -1.005691 -0.248509 1.047982 C 0.306427 -0.559530 0.715006 C 0.499133 -0.983910 -0.595701 C -0.531367 -1.097493 -1.517545 C -1.823400 -0.779750 -1.134046 C -2.064879 -0.350487 0.160706 B 1.571460 -0.466740 1.707497 C 2.034513 0.975196 2.209242 C 1.287246 2.112700 1.896272 C 1.626269 3.379404 2.360101 C 2.743026 3.530600 3.164972 C 3.525115 2.423399 3.473922 C 3.191739 1.155807 2.999052 N 3.988077 0.017310 3.324186 C 4.649138 0.040998 4.612737 F 1.723766 -1.306257 -1.028323 F -0.293383 -1.509194 -2.760687 F -2.823978 -0.883228 -2.001314 F -3.303773 -0.039822 0.536116 F -1.304621 0.180962 2.284296 C 4.912451 -0.362820 2.264830 C 0.902473 -1.057196 3.692528 C 1.135720 -2.028045 3.004588 H 5.297126 -1.369184 2.455798 H 4.996553 -0.968822 4.848409 H 5.527092 0.709589 4.653599 H 3.947685 0.348633 5.391132 H 4.404047 -0.367342 1.302115 H 5.769677 0.329433 2.201185 H 4.409522 2.554290 4.086737 H 3.019137 4.508239 3.544806 H 1.014285 4.236002 2.101298 H 0.400739 2.008980 1.279998 H 2.459591 -1.181911 1.357640 C 0.593142 -0.016296 4.663260 C 1.339235 -3.322174 2.361436 H 0.833206 -3.349150 1.394080 H 2.404202 -3.495525 2.197116 H 0.936370 -4.115233 2.994112 H 0.034280 -0.458504 5.490849 H 1.512530 0.431165 5.044006




105

H -0.007881 0.768308 4.204537 42 TShydr(b)

C 0.049228 -0.063224 -0.007753 C -0.005307 0.018162 1.374923 C -1.272795 -0.156888 1.923649 C -2.405657 -0.414528 1.170881 C -2.296733 -0.494433 -0.208633 C -1.060708 -0.314976 -0.802884 B 1.215148 0.292108 2.406838 C 1.540903 -0.849978 3.486798 C 1.414877 -2.189460 3.115367 C 1.813572 -3.230379 3.946920 C 2.356763 -2.937954 5.188045 C 2.474721 -1.613709 5.593642 C 2.069318 -0.571939 4.759933 N 2.165536 0.794603 5.179696 C 3.270336 1.113361 6.061597 F -1.438800 -0.069444 3.250613 F -3.592538 -0.575791 1.751352 F -3.370639 -0.737289 -0.952638 F -0.944900 -0.385669 -2.127905 F 1.211783 0.105014 -0.661430 C 0.902649 1.307156 5.695383 C 2.726817 0.605007 1.663878 C 2.402143 1.691469 2.168716 H 0.958428 2.396233 5.796425 H 3.380748 2.201214 6.113819 H 3.137076 0.749603 7.094993 H 4.196045 0.694068 5.663367 H 0.089771 1.062691 5.011398 H 0.656665 0.883091 6.683398 H 2.880171 -1.395068 6.574984 H 2.679078 -3.735045 5.848938 H 1.707497 -4.259556 3.622433 H 1.004663 -2.425365 2.136923 H 0.897287 1.328320 2.978841 C 3.648566 -0.354367 1.034474 C 2.414008 3.077722 2.643740 H 1.566428 3.638837 2.246441 H 2.378660 3.085966 3.734420 H 3.338933 3.550495 2.305795 H 4.590473 0.127783 0.769959 H 3.840725 -1.167795 1.738423 H 3.197738 -0.780043 0.138816 42 int1'

C 0.034646 0.505635 0.112004 C -0.018911 0.270653 1.491805 C -1.218514 0.586308 2.175402 C -2.276321 1.171174 1.475252 C -2.169369 1.428712 0.114209 C -1.019194 1.087359 -0.580233 B 1.303443 -0.119724 2.218979 C 1.658307 0.589980 3.598878 C 1.564837 1.965935 3.766786 C 1.842773 2.593479 4.969409 C 2.222826 1.830113 6.062650 C 2.328835 0.454664 5.938127 C 2.057274 -0.133837 4.713778 F 1.199225 2.742996 2.744732




106

F 2.151939 -1.469472 4.646646 F 2.683997 -0.282111 6.988152 F 2.484504 2.415859 7.224880 F 1.746188 3.915122 5.089414 N -1.311204 0.322310 3.552108 C -2.332969 1.008631 4.310435 C -1.127138 -1.050273 3.993939 C 2.312328 -1.141774 1.629926 C 3.778962 -1.101569 2.010249 C 1.811898 -2.140186 0.876269 C 2.553044 -3.322035 0.338529 H -2.101725 0.910993 5.374116 H -0.756254 -1.065044 5.022982 H -2.072019 -1.616218 3.957237 H -0.401762 -1.570514 3.369478 H -2.336112 2.071071 4.061705 H -3.345875 0.602334 4.149143 H -3.199002 1.416273 1.985701 H -3.004481 1.885534 -0.405957 H -0.937527 1.281719 -1.643012 H 0.949705 0.266885 -0.419129 H 0.750264 -2.117428 0.639268 H 2.488612 -3.343070 -0.754799 H 3.605203 -3.332785 0.623256 H 2.091787 -4.249063 0.694436 H 4.424151 -1.258045 1.141820 H 4.049057 -0.138482 2.447511 H 4.021004 -1.872111 2.748636 42 int1

C -1.185739 0.268754 1.734349 C 0.150187 0.084117 1.401786 C 0.588671 0.814969 0.306385 C -0.212602 1.694273 -0.402680 C -1.535373 1.854585 -0.024439 C -2.027961 1.132562 1.049510 B 1.059299 -0.986865 2.203749 C 1.322250 -2.354366 1.416817 C 1.251394 -3.520469 2.074410 F 1.862169 0.695878 -0.120180 F 0.271050 2.378488 -1.437512 F -2.325586 2.689310 -0.690493 F -3.301173 1.271740 1.410379 F -1.731268 -0.417723 2.745263 C 0.929563 -1.090544 3.802506 C 2.189274 -0.591312 4.042057 C 2.790851 -0.485535 5.282074 C 2.022978 -0.926398 6.357488 C 0.735507 -1.429895 6.159542 C 0.174098 -1.519709 4.886964 N 2.655459 -0.205926 2.710710 C 3.885602 -0.886318 2.278438 C 2.803086 1.258887 2.614901 H 3.078604 1.533425 1.599093 H 4.076888 -0.633932 1.234614 H 4.735500 -0.569488 2.891141 H 3.744455 -1.962093 2.369064 H 1.855728 1.728953 2.877301 H 3.576311 1.601672 3.309209 H 3.789516 -0.087898 5.425430 H 2.427753 -0.874789 7.361774 H 0.163972 -1.758543 7.020838




107

H -0.826633 -1.914680 4.756560 C 1.578384 -2.325815 -0.072252 C 1.403552 -4.896900 1.477882 H 1.057107 -3.493910 3.143451 H 1.267171 -5.668878 2.237094 H 0.669516 -5.078649 0.686488 H 2.394819 -5.041748 1.035405 H 1.753047 -3.317704 -0.492652 H 0.725654 -1.887873 -0.602408 H 2.442827 -1.702162 -0.316463 42 int2'

C -0.844332 0.432496 -2.205565 C 0.140932 -0.134423 -1.409310 C 0.302727 0.420835 -0.146757 C -0.460677 1.482958 0.307171 C -1.423691 2.031235 -0.526199 C -1.616729 1.506838 -1.793552 B 1.067632 -1.320877 -1.924395 C 0.407440 -2.633417 -2.429676 C -0.809737 -2.951200 -1.950267 F 1.221071 -0.073621 0.687292 F -0.280922 1.983495 1.526916 F -2.159224 3.055367 -0.109924 F -2.533195 2.038879 -2.599295 F -1.050839 -0.023023 -3.448416 C 2.614186 -1.160152 -1.814684 C 3.334770 -2.261695 -1.336657 C 4.659381 -2.161632 -0.935382 C 5.297349 -0.934189 -1.035499 C 4.630541 0.169892 -1.550220 C 3.295824 0.072564 -1.953413 N 2.607544 1.178676 -2.477315 C 3.155229 2.496468 -2.244876 C 2.034595 1.049161 -3.807175 H 1.171891 1.713401 -3.910698 H 2.385909 3.238165 -2.473567 H 4.034922 2.721822 -2.871229 H 3.431773 2.609810 -1.195462 H 1.696840 0.029742 -3.989354 H 2.767560 1.306892 -4.588624 H 5.164033 1.106533 -1.649865 H 6.332952 -0.832445 -0.729247 H 5.182024 -3.025551 -0.542575 H 2.823635 -3.213142 -1.228590 C 1.138107 -3.564444 -3.378729 C -1.582322 -4.202986 -2.213592 H -1.303179 -2.241869 -1.288581 H 0.521694 -3.792335 -4.253240 H 2.067272 -3.118550 -3.735699 H 1.395380 -4.518039 -2.905452 H -1.852902 -4.689341 -1.270965 H -2.522976 -3.961131 -2.720640 H -1.036294 -4.919689 -2.827323 42 int2 C 0.029377 0.015094 -0.004688 C 0.018515 0.014612 1.382873 C -1.237269 -0.080561 1.966012 C -2.411648 -0.198055 1.242105 C -2.350543 -0.205314 -0.142161




108

C -1.122098 -0.093123 -0.771346 B 1.373014 0.177935 2.241803 C 1.563638 1.589535 2.969941 C 0.595952 2.516027 2.974784 F -1.357587 -0.064505 3.307936 F -3.588928 -0.299124 1.856246 F -3.463432 -0.313514 -0.859909 F -1.059574 -0.087675 -2.100719 F 1.182357 0.143688 -0.671499 C 2.733841 -0.528116 1.748118 C 2.760151 -1.437087 2.782680 C 3.785745 -2.324744 3.048398 C 4.864948 -2.268427 2.168763 C 4.873226 -1.368429 1.100789 C 3.815298 -0.488346 0.877930 N 1.478775 -1.212193 3.449575 C 1.552850 -0.858661 4.875481 C 0.576492 -2.363272 3.253350 H -0.401518 -2.133466 3.672506 H 0.586646 -0.456445 5.181155 H 1.794107 -1.740732 5.477406 H 2.317772 -0.101268 5.026452 H 0.481227 -2.566030 2.187494 H 0.988530 -3.246731 3.750842 H 3.767464 -3.021257 3.879374 H 5.708683 -2.933619 2.312725 H 5.728805 -1.356351 0.434162 H 3.846241 0.205069 0.045465 C 2.904326 1.951910 3.583869 C 0.725359 3.890842 3.569872 H -0.358882 2.289703 2.509798 H -0.158477 4.499472 3.372939 H 0.862701 3.844475 4.656629 H 1.596196 4.420027 3.167432 H 3.380595 2.765269 3.024070 H 2.796391 2.305636 4.615978 H 3.608400 1.117750 3.582846 44 TSsplit

C 2.751427 -1.594717 0.147654 C 1.994528 -0.486336 -0.246850 C 2.423449 0.778394 0.182551 C 3.568682 0.914298 0.965226 C 4.295428 -0.203233 1.347912 C 3.882057 -1.465127 0.940340 B 0.700599 -0.729647 -1.144554 C 0.788248 -1.818918 -2.281748 C -0.229640 -2.671182 -2.464511 N 1.663198 1.930573 -0.225100 C 2.457818 3.028826 -0.755573 C -0.738357 -0.423987 -0.497958 C -1.047422 -0.881183 0.777514 C -2.267878 -0.643893 1.390657 C -3.237482 0.078347 0.714534 C -2.979198 0.537390 -0.566415 C -1.751196 0.267694 -1.150286 F -0.152477 -1.590820 1.471610 F -1.567974 0.722433 -2.395938 F -3.911253 1.221464 -1.225001 F -4.411325 0.318812 1.285946 F -2.516769 -1.101899 2.614440 C 0.721975 2.386567 0.792186




109

H 1.790384 3.748759 -1.236585 H 0.036465 3.116519 0.352971 H 1.233853 2.856323 1.647203 H 0.138633 1.544343 1.162662 H 3.154849 2.648498 -1.504343 H 3.031589 3.565737 0.015735 H 3.890402 1.899736 1.284334 H 5.180714 -0.088407 1.963295 H 4.443855 -2.344680 1.233730 H 2.438795 -2.583315 -0.173741 C 2.064956 -1.921139 -3.094584 C -0.277407 -3.823266 -3.419991 H -1.125871 -2.542550 -1.860314 H 0.957376 0.970507 -1.759082 H 0.775605 0.483573 -2.342468 H 1.856356 -1.931650 -4.168403 H 2.732011 -1.080319 -2.892524 H 2.624374 -2.832485 -2.860008 H -0.480446 -4.756318 -2.884332 H -1.094749 -3.689831 -4.136973 H 0.650275 -3.948046 -3.979801 44 intH2

C 2.417818 -1.845498 0.232364 C 1.924472 -0.619082 -0.230445 C 2.464150 0.501565 0.392251 C 3.416208 0.471290 1.401824 C 3.873175 -0.765459 1.829113 C 3.370451 -1.922217 1.237793 B 0.779464 -0.471454 -1.392995 C 0.833748 -1.647641 -2.493210 C -0.205438 -2.436641 -2.785382 N 1.939023 1.800196 -0.086906 C 2.982058 2.699566 -0.633880 C -0.670123 -0.245576 -0.657369 C -1.239367 -1.201925 0.177192 C -2.459450 -1.035279 0.814969 C -3.161925 0.147012 0.644944 C -2.629206 1.140279 -0.157689 C -1.411276 0.920732 -0.784193 F -0.607165 -2.360198 0.402440 F -0.933529 1.960202 -1.508338 F -3.279512 2.295918 -0.307918 F -4.329943 0.329710 1.255938 F -2.961128 -1.992056 1.594532 C 1.056347 2.469615 0.900506 H 2.498594 3.571857 -1.073751 H 0.555453 3.307965 0.417414 H 1.657866 2.813382 1.741741 H 0.319958 1.744343 1.240702 H 3.534976 2.152226 -1.395384 H 3.655978 3.009024 0.163713 H 3.796073 1.381500 1.854772 H 4.614484 -0.826377 2.616869 H 3.726162 -2.891067 1.570574 H 2.028148 -2.753612 -0.215339 C 2.154509 -1.738905 -3.225129 C -0.307069 -3.530270 -3.811325 H -1.128722 -2.285642 -2.227697 H 1.358779 1.492511 -0.906482 H 1.027848 0.569998 -2.028131 H 2.207664 -2.545103 -3.959106




110

H 2.352205 -0.796802 -3.750544 H 2.982526 -1.878038 -2.521038 H -0.585683 -4.477778 -3.336877 H -1.092995 -3.302533 -4.540363 H 0.618360 -3.695965 -4.364548 44 intH2

prot

C 1.874791 -1.088485 1.250265 C 1.104564 -0.397825 0.324068 C 1.777389 0.598021 -0.374370 C 3.115442 0.902654 -0.180346 C 3.842923 0.182561 0.752818 C 3.218669 -0.820001 1.474236 B -0.457449 -0.755814 0.026864 C -0.579737 -1.293864 -1.518958 C 0.036675 -2.654473 -1.741745 F 1.121528 1.339519 -1.281911 F 3.708134 1.875419 -0.875554 F 5.130697 0.455391 0.956056 F 3.915344 -1.515675 2.375137 F 1.341984 -2.074170 1.986219 C -1.467953 0.468147 0.415680 C -1.072107 1.667783 1.021680 C -1.979886 2.638033 1.423265 C -3.344739 2.450083 1.237594 C -3.789140 1.279930 0.641383 C -2.847024 0.341086 0.247286 N -3.305311 -0.931942 -0.363303 C -3.690930 -1.933187 0.664882 C -1.116019 -0.573124 -2.517772 C -1.215615 -0.904162 -3.980795 C -4.332754 -0.777727 -1.420024 H -4.450091 -1.734357 -1.929046 H -4.576942 -1.573758 1.187970 H -2.856431 -2.040382 1.354352 H -3.898292 -2.884780 0.174449 H -3.989260 -0.022576 -2.123915 H -5.281094 -0.478307 -0.977301 H -4.851308 1.117480 0.494434 H -4.056664 3.203450 1.552510 H -1.621254 3.549903 1.887811 H -0.015287 1.839308 1.191928 H -1.476919 0.426228 -2.265810 H -2.449914 -1.270593 -0.858347 H -0.771076 -1.692985 0.749465 H -0.020777 -3.020471 -2.769002 H 1.094570 -2.621839 -1.460176 H -0.423836 -3.396029 -1.080342 H -2.217087 -0.685660 -4.368327 H -0.517982 -0.285578 -4.556014 H -0.991645 -1.948189 -4.203278 44 TS

prot

C -1.198404 1.701121 1.151875 C -1.582887 0.485998 0.579519 C -2.950357 0.326371 0.322113 C -3.888013 1.315762 0.592850 C -3.467602 2.511407 1.158680 C -2.119929 2.698752 1.442576 B -0.591228 -0.731161 0.240233 C -0.901079 -1.382346 -1.398535




111

C -0.926385 -0.479620 -2.403270 N -3.332721 -0.951241 -0.249978 C -4.273594 -0.882503 -1.363241 C 0.996210 -0.406819 0.261591 C 1.587983 0.616510 -0.470119 C 2.948808 0.875185 -0.472495 C 3.787404 0.081751 0.292664 C 3.249598 -0.952586 1.038775 C 1.879969 -1.178097 1.009298 F 0.832510 1.417911 -1.241557 F 1.438234 -2.202483 1.747929 F 4.052509 -1.721560 1.773437 F 5.097295 0.311175 0.308089 F 3.456489 1.870906 -1.199481 C -3.733299 -1.935509 0.761648 H -4.325441 -1.863821 -1.840651 H -4.706114 -1.675481 1.196957 H -2.981237 -1.963119 1.547920 H -3.799603 -2.922521 0.297890 H -3.914545 -0.154951 -2.092329 H -5.281869 -0.597902 -1.041766 H -4.939168 1.157987 0.376256 H -4.189186 3.289345 1.380233 H -1.786220 3.629885 1.887149 H -0.149967 1.870485 1.374934 C -0.364585 -2.783992 -1.580656 C -0.380776 -0.630191 -3.780138 H -1.353209 0.496589 -2.178372 H -2.023574 -1.272211 -0.813044 H -0.822293 -1.677124 0.953084 H -0.671907 -3.235689 -2.528340 H 0.729552 -2.789554 -1.546028 H -0.707945 -3.425532 -0.766918 H -1.120136 -0.334820 -4.530751 H 0.465984 0.057323 -3.891297 H -0.033508 -1.640617 -3.995266 44 TSAr-prot

C -2.925955 1.692422 0.276207 C -2.137603 0.644088 -0.210902 C -2.712089 -0.630276 -0.171256 C -3.980306 -0.871287 0.340306 C -4.733096 0.194238 0.813468 C -4.204029 1.478709 0.774933 B -0.696637 0.920399 -0.843782 C 0.140440 2.171624 -0.357244 C 0.788970 2.895461 -1.281033 N -1.886444 -1.708567 -0.684817 C -2.090485 -1.968596 -2.117494 C -1.877316 -2.933860 0.118119 C 0.490232 -0.612829 -0.244702 C 0.799481 -0.614819 1.109263 C 2.094883 -0.657278 1.590333 C 3.136740 -0.752223 0.679014 C 2.875173 -0.822165 -0.683539 C 1.562948 -0.773525 -1.114127 F -0.192163 -0.556164 2.009950 F 1.344585 -0.856644 -2.429517 F 3.886511 -0.943991 -1.540265 F 4.388856 -0.799523 1.111861 F 2.357776 -0.613343 2.894300 H -1.291622 -2.620016 -2.478310




112

H -1.049694 -3.561888 -0.218905 H -2.809771 -3.496787 0.016961 H -1.722266 -2.668332 1.163561 H -2.046047 -1.023956 -2.656209 H -3.061062 -2.445652 -2.287613 H -4.387374 -1.876100 0.365453 H -5.727804 0.020976 1.207456 H -4.788599 2.315162 1.141521 H -2.523271 2.699954 0.259109 C 0.210990 2.538773 1.114478 C 1.623747 4.120383 -1.054151 H 0.719714 2.570579 -2.318024 H -0.693116 -1.157709 -0.549033 H -0.637305 0.696793 -2.025598 H 2.651972 3.949130 -1.392073 H 1.240835 4.965502 -1.636346 H 1.661508 4.418882 -0.005385 H -0.030974 3.591624 1.290044 H -0.480018 1.942239 1.711853 H 1.216739 2.371538 1.517178 32 prodAr-prot C -5.012362 1.228165 0.834795 C -3.996441 1.914047 0.167872 C -2.936743 1.182613 -0.354907 C -2.947247 -0.186752 -0.178310 C -3.929084 -0.911509 0.469158 C -4.984122 -0.159485 0.984554 B -1.538362 1.176283 -1.158720 C -0.210909 1.768549 -0.513794 C -0.129894 2.032602 0.980534 N -1.707924 -0.600401 -0.832567 C -0.718019 -1.208942 0.064755 C 0.829440 2.039719 -1.313756 C 2.162408 2.601547 -0.913484 C -1.912001 -1.415524 -2.036805 H -0.965921 -1.491454 -2.575684 H 0.255317 -1.204150 -0.428905 H -1.001876 -2.236568 0.315738 H -0.651533 -0.621391 0.978539 H -2.645300 -0.925027 -2.675104 H -2.264786 -2.418711 -1.773469 H -3.893712 -1.989824 0.581035 H -5.791649 -0.656905 1.509678 H -5.848099 1.781355 1.250364 H -4.046621 2.993357 0.068910 H 0.709052 1.854387 -2.380277 H -1.601936 1.264821 -2.363025 H 2.974867 1.935011 -1.223748 H 2.340903 3.562154 -1.409427 H 2.248122 2.758923 0.163024 H 0.030664 3.095095 1.192429 H -1.054615 1.744707 1.486817 H 0.693532 1.486467 1.455290 44 TSadd C -0.002704 -0.006154 -0.003692 C 0.006439 -0.002892 1.394020 C -1.013321 0.738826 2.032619 C -1.920018 1.486298 1.278048 C -1.863619 1.496747 -0.108047




113

C -0.908948 0.730832 -0.756356 B 1.072412 -0.840093 2.245629 C 1.625361 -0.321709 3.654375 C 1.805846 1.023771 3.958535 C 2.188392 1.475580 5.206473 C 2.422134 0.555550 6.218917 C 2.267371 -0.794399 5.963466 C 1.873181 -1.205245 4.696228 F 1.618019 1.954248 3.016216 F 1.720473 -2.525632 4.525513 F 2.489364 -1.683297 6.930244 F 2.797419 0.971355 7.423250 F 2.339214 2.776970 5.448034 N -1.093578 0.725418 3.448304 C -1.651328 1.887995 4.100131 C -1.546194 -0.518942 4.042090 C 2.690695 -1.663262 1.028252 C 2.999141 -0.348447 1.121449 H -1.371602 1.864054 5.157881 H -1.251245 -0.551554 5.095957 H -2.641673 -0.633272 3.983536 H -1.091870 -1.373702 3.539726 H -1.233184 2.795035 3.660710 H -2.752788 1.943439 4.050018 H -2.688326 2.061097 1.781343 H -2.575559 2.087110 -0.674117 H -0.860055 0.709568 -1.839138 H 0.739176 -0.583328 -0.547186 H 0.854698 -2.019399 2.271235 C 4.105178 0.230186 1.947791 H 2.519515 0.338714 0.433317 H 2.016057 -1.973550 0.237412 C 3.378786 -2.772974 1.764175 H 3.866138 1.244409 2.266541 H 4.340985 -0.370621 2.826132 H 5.005524 0.285769 1.325975 H 4.233328 -3.120983 1.174843 H 3.748255 -2.458636 2.740425 H 2.703014 -3.614880 1.914274 44 cat'(a)⋅⋅⋅but-2-ene C -0.007810 -0.024195 0.002109 C -0.000634 -0.002169 1.399904 C -1.049931 0.711057 2.022492 C -1.987003 1.405176 1.254560 C -1.934685 1.391044 -0.131672 C -0.946576 0.656230 -0.764601 B 1.108046 -0.783932 2.269595 C 1.586640 -0.219983 3.698127 C 1.754794 1.136349 3.952803 C 2.053270 1.644741 5.201751 C 2.215657 0.771673 6.268358 C 2.072269 -0.587761 6.063114 C 1.760776 -1.054272 4.791944 F 1.620346 2.022037 2.957915 F 1.611238 -2.382820 4.670914 F 2.225302 -1.433770 7.080937 F 2.511332 1.241237 7.475945 F 2.186937 2.956317 5.394553 N -1.131025 0.729909 3.439768 C -1.694923 1.905770 4.061930 C -1.588899 -0.502227 4.053402




114

C 2.496587 -1.768950 1.183087 C 2.864932 -0.456733 1.242271 H -1.413727 1.911375 5.119747 H -1.321016 -0.505025 5.115001 H -2.681807 -0.627956 3.970553 H -1.113075 -1.363812 3.584122 H -1.282547 2.803259 3.597840 H -2.796862 1.954800 4.012601 H -2.776318 1.958730 1.749509 H -2.671617 1.939149 -0.708080 H -0.894536 0.617292 -1.846830 H 0.760354 -0.572027 -0.536725 H 0.804446 -1.943702 2.405619 C 4.029433 0.076934 2.022211 H 2.454081 0.221440 0.503984 H 1.829887 -2.073277 0.383372 C 3.166233 -2.884949 1.927679 H 3.864687 1.115196 2.308220 H 4.249960 -0.503864 2.917098 H 4.911517 0.048834 1.373296 H 4.030354 -3.225818 1.348340 H 3.517749 -2.575314 2.911206 H 2.486277 -3.725995 2.060359 44 TShydr

C -0.017992 -0.033056 -0.006738 C -0.003923 0.001079 1.390898 C -1.131602 0.573985 2.017635 C -2.156789 1.135111 1.253538 C -2.116381 1.113989 -0.132861 C -1.046462 0.507317 -0.769290 B 1.233037 -0.597980 2.239828 C 1.555573 -0.096865 3.733439 C 1.642863 1.257907 4.029790 C 1.828669 1.744059 5.309076 C 1.954266 0.849746 6.363390 C 1.882045 -0.508325 6.116254 C 1.682016 -0.951602 4.815127 F 1.515135 2.159149 3.048201 F 1.583360 -2.282732 4.648138 F 1.993222 -1.375300 7.121915 F 2.142006 1.298543 7.600667 F 1.884932 3.054138 5.543864 N -1.210441 0.581593 3.436935 C -1.882052 1.699405 4.060092 C -1.571739 -0.691282 4.030969 C 2.492008 -1.668806 1.311501 C 2.777900 -0.306382 1.315853 H -1.604875 1.729622 5.118604 H -1.334275 -0.678283 5.099624 H -2.645718 -0.917034 3.915940 H -1.004306 -1.500854 3.570143 H -1.552981 2.631482 3.597621 H -2.983858 1.647722 4.008329 H -3.006165 1.586731 1.752908 H -2.923296 1.555978 -0.706641 H -0.999801 0.464616 -1.851660 H 0.813403 -0.476998 -0.548209 H 1.028639 -1.804098 2.344321 C 3.953456 0.296973 2.042809 H 2.439247 0.268494 0.462661 H 1.903363 -2.051116 0.483131




115

C 3.270252 -2.701090 2.073886 H 3.766295 1.347669 2.264954 H 4.185825 -0.211102 2.978433 H 4.837100 0.243639 1.398991 H 4.164287 -2.945816 1.491662 H 3.590275 -2.339568 3.049599 H 2.687791 -3.610657 2.218011 44 int’

C 0.231822 -0.543255 0.111275 C -0.073199 0.155662 1.306294 C -1.391021 0.098033 1.778939 C -2.367086 -0.671027 1.161319 C -2.033536 -1.391385 0.024501 C -0.751811 -1.320454 -0.504899 B 1.008302 0.799954 2.225106 C 2.431346 0.090953 2.327822 C 3.632697 0.739824 2.093621 C 4.861201 0.103008 2.156419 C 4.908764 -1.238732 2.496031 C 3.731675 -1.922182 2.760225 C 2.523902 -1.252418 2.668807 F 3.639077 2.036879 1.743701 F 1.415155 -1.948814 2.939667 F 3.776006 -3.208284 3.096237 F 6.075662 -1.867230 2.570815 F 5.986263 0.762904 1.893896 N 1.527239 -0.449034 -0.423943 C 1.960620 -1.476736 -1.344581 C 1.996763 0.870427 -0.814930 H 1.527294 -1.372560 -2.353588 H 3.088852 0.907719 -0.771002 H 1.681570 1.123236 -1.840151 H 1.606578 1.637882 -0.147847 H 1.708463 -2.463298 -0.952704 H 3.047593 -1.419238 -1.442914 H -0.527416 -1.861997 -1.415028 H -2.780084 -2.001728 -0.472147 H -3.369446 -0.717052 1.569798 H -1.649776 0.627300 2.689221 H 2.617683 2.433259 4.000001 C 0.689861 2.101209 3.067315 C 1.567417 2.356502 4.299064 H -0.345905 2.012715 3.422959 H 1.305785 3.333484 4.723046 C 0.697534 3.310039 2.102557 H 0.392228 4.216201 2.634133 H 1.695140 3.488218 1.694193 H 0.005843 3.160712 1.269031 C 1.409636 1.288170 5.378287 H 1.688555 0.297318 5.007758 H 2.036755 1.503136 6.246863 H 0.371796 1.231378 5.721431 44 int

C 0.179888 -1.622485 4.787643 C 0.943427 -1.129217 3.737029 C 2.196939 -0.636633 4.022133 C 2.787345 -0.597233 5.270421 C 2.010918 -1.105478 6.310158 C 0.728989 -1.603500 6.069188




116

B 1.130249 -0.955956 2.145637 N 2.663955 -0.172640 2.713976 C 2.723600 1.304185 2.687110 C 0.217288 0.097277 1.326437 C -1.131113 0.256274 1.618851 C -1.971673 1.094733 0.901233 C -1.462671 1.820143 -0.162612 C -0.124707 1.689749 -0.496890 C 0.673817 0.832832 0.241786 F -1.691570 -0.432084 2.621502 F 1.965152 0.747623 -0.136471 F 0.375571 2.381308 -1.518783 F -2.250566 2.631680 -0.859460 F -3.258294 1.206987 1.221877 C 1.377358 -2.359313 1.376679 C 0.043945 -3.136078 1.401940 C 3.953198 -0.740657 2.288512 H 2.987146 1.640420 1.686556 H 4.159223 -0.421951 1.266811 H 4.755877 -0.391711 2.945466 H 3.902545 -1.826742 2.327006 H 1.749112 1.703579 2.964529 H 3.472484 1.655927 3.402713 H 3.781491 -0.201691 5.447112 H 2.404910 -1.110285 7.319965 H 0.150699 -1.984421 6.904037 H -0.820025 -2.009569 4.628407 H 2.082606 -2.952409 1.978515 C 1.924944 -2.268760 -0.052101 C 0.141393 -4.584171 0.923675 H -0.354011 -3.133580 2.421686 H -0.692521 -2.603215 0.786602 H 2.149774 -3.257565 -0.461749 H 1.194506 -1.797991 -0.718795 H 2.841008 -1.678549 -0.111657 H -0.814984 -5.099824 1.045319 H 0.415709 -4.649808 -0.132150 H 0.893183 -5.133650 1.499512 46 TSsplit C -1.555027 0.609069 -0.855721 C -0.662363 -0.397359 -0.517477 C -1.066355 -1.236703 0.512584 C -2.260058 -1.083150 1.198237 C -3.107917 -0.045186 0.847713 C -2.752974 0.805410 -0.185814 B 0.779497 -0.697871 -1.160689 C 0.850418 -1.698514 -2.397331 C -0.401928 -1.672554 -3.290404 F -0.278881 -2.260031 0.874003 F -2.598908 -1.917126 2.176688 F -4.256838 0.126462 1.490654 F -3.563651 1.803483 -0.528225 F -1.281696 1.468428 -1.845482 C 2.018480 -0.516040 -0.185203 C 2.823167 -1.617113 0.129624 C 3.885519 -1.517047 1.016271 C 4.177980 -0.293636 1.604871 C 3.398364 0.814746 1.307970 C 2.322050 0.707611 0.429936 N 1.503136 1.850590 0.119690 C 0.580004 2.197512 1.192964




117

C 2.250298 3.009492 -0.346774 H 1.547880 3.748880 -0.740840 H -0.154938 2.916778 0.820230 H 1.092910 2.640624 2.062159 H 0.049783 1.305267 1.528089 H 2.924749 2.710822 -1.151949 H 2.846023 3.495012 0.442623 H 3.622700 1.770795 1.769170 H 5.008870 -0.202794 2.295476 H 4.486178 -2.390187 1.244262 H 2.608238 -2.579340 -0.323561 H 1.032583 1.093712 -1.775633 H 1.036621 0.672603 -2.413724 H 0.859636 -2.680703 -1.889714 C 2.143122 -1.589944 -3.218198 C -0.436805 -2.751561 -4.370666 H -0.483373 -0.684394 -3.762747 H -1.291238 -1.777778 -2.661053 H 2.282907 -2.451516 -3.875325 H 2.115371 -0.697780 -3.855454 H 3.026183 -1.510987 -2.581494 H -1.391186 -2.738181 -4.903032 H 0.353993 -2.614343 -5.112255 H -0.313139 -3.746560 -3.930811 46 intH2

C -1.353011 0.896512 -0.781478 C -0.632426 -0.286913 -0.725087 C -1.269160 -1.314908 -0.039329 C -2.524648 -1.194303 0.535101 C -3.200719 0.012637 0.446463 C -2.606615 1.072998 -0.214278 B 0.848642 -0.487147 -1.412514 C 0.903239 -1.682816 -2.517089 F -0.667231 -2.506474 0.090460 F -3.087594 -2.217848 1.175472 F -4.403486 0.152300 0.998862 F -3.236163 2.247042 -0.292521 F -0.827822 1.990429 -1.387291 C 1.952498 -0.627602 -0.211992 C 2.415183 -1.848708 0.297235 C 3.341487 -1.916599 1.327786 C 3.851616 -0.755022 1.901678 C 3.425217 0.476672 1.431541 C 2.497137 0.497810 0.399660 N 2.006890 1.795780 -0.115092 C 1.150838 2.517507 0.858257 C 3.074856 2.646192 -0.691812 H 2.617429 3.523771 -1.148722 H 0.676138 3.360216 0.357813 H 1.766280 2.859640 1.689995 H 0.392157 1.825141 1.218049 H 3.601151 2.061694 -1.444668 H 3.766266 2.950402 0.092791 H 3.809893 1.392339 1.869322 H 4.573536 -0.808090 2.707721 H 3.671485 -2.883249 1.691961 H 2.030505 -2.766960 -0.131240 H 1.415752 1.484021 -0.924992 H 1.092894 0.555021 -2.047400 C 2.277377 -1.716217 -3.198296 H 0.752831 -2.651674 -2.018124




118

C -0.225100 -1.536429 -3.549891 C -0.305994 -2.655657 -4.587872 H -1.185051 -1.483742 -3.023484 H -0.111968 -0.571005 -4.062399 H 2.392841 -2.564293 -3.880906 H 2.434086 -0.799442 -3.780630 H 3.087657 -1.780222 -2.465310 H -1.182997 -2.536498 -5.230866 H 0.574335 -2.676584 -5.236035 H -0.380797 -3.632601 -4.098605 46 TSprot

C 3.267353 -2.007014 -1.438919 C 2.639484 -0.772249 -1.545120 C 3.269410 0.272587 -0.879873 C 4.440529 0.125608 -0.155536 C 5.030795 -1.125888 -0.077929 C 4.441085 -2.199725 -0.722148 B 1.246250 -0.596497 -2.354483 C 0.042797 -0.096234 -1.416395 C 0.048865 -0.115152 -0.019088 C -1.046544 0.315833 0.717690 C -2.183875 0.791360 0.074398 C -2.225685 0.825185 -1.312666 C -1.121315 0.374053 -2.022339 N -1.067960 0.353503 -3.472675 C -1.594829 -0.908278 -4.027873 F 2.738491 1.504583 -0.925090 F 5.002219 1.163703 0.462223 F 6.155788 -1.292792 0.610534 F 5.006051 -3.403931 -0.648960 F 2.751892 -3.089236 -2.032635 C -1.695136 1.510102 -4.124385 C 1.606731 0.591080 -3.824709 C 1.502242 0.096790 -5.280410 H -1.393063 1.535428 -5.172528 H -1.387418 -0.942859 -5.098742 H -2.675382 -0.970022 -3.860645 H -1.101968 -1.746874 -3.541486 H -1.368138 2.424743 -3.633598 H -2.787308 1.444611 -4.078914 H -3.109391 1.193158 -1.821887 H -3.036459 1.133387 0.649552 H -1.012550 0.288650 1.801114 H 0.929002 -0.474081 0.504114 H 0.292189 0.323887 -3.551609 H 0.985773 -1.607485 -2.953901 H 2.612415 0.303779 -3.523607 C 1.525957 2.122030 -3.684270 C 2.640914 0.592490 -6.168843 H 0.548971 0.416684 -5.721361 H 1.490137 -0.997708 -5.273339 H 2.495326 2.595781 -3.853187 H 0.830046 2.548145 -4.413329 H 1.193274 2.409876 -2.684979 H 2.545585 0.205984 -7.186834 H 2.655585 1.684291 -6.227180 H 3.608444 0.266818 -5.775202 38 TShydr

C -0.424547 -0.175642 -0.054911




119

C 0.049896 0.180882 1.205761 C -0.796361 1.000139 1.948820 C -2.026101 1.441397 1.489070 C -2.451544 1.064356 0.225321 C -1.646587 0.250628 -0.553791 B 1.486241 -0.336127 1.677637 C 2.553011 0.655136 2.298520 C 3.745664 0.217841 2.916088 C 4.641894 1.144570 3.445594 C 4.401805 2.509187 3.342589 C 3.261921 2.959413 2.697162 C 2.355645 2.035572 2.192486 N 4.007699 -1.184990 3.005025 C 4.733954 -1.626123 4.181186 F -0.449905 1.389692 3.182518 F -2.799189 2.217359 2.243793 F -3.624338 1.479874 -0.233952 F -2.052376 -0.113141 -1.766971 F 0.302174 -0.957630 -0.857063 C 4.591039 -1.734477 1.787305 C 0.851202 -1.271883 3.773168 C 1.035439 -2.272830 2.904158 H 4.556614 -2.827802 1.824348 H 4.643728 -2.713113 4.264160 H 5.810536 -1.386478 4.155850 H 4.301797 -1.177655 5.077847 H 4.028488 -1.402987 0.915776 H 5.642200 -1.426280 1.660321 H 5.546976 0.801958 3.933215 H 5.114024 3.214199 3.756980 H 3.067926 4.021276 2.598941 H 1.460267 2.406115 1.705962 H 1.895036 -1.232621 1.007457 H 2.004006 -2.746610 2.811899 H 0.218745 -2.662770 2.306574 H -0.119065 -0.820536 3.931816 H 1.665309 -0.919901 4.393407 38 int’

C 0.441277 0.510448 0.290807 C 0.117666 -0.055796 1.514546 C -1.224106 -0.337741 1.724614 C -2.204514 -0.059132 0.786423 C -1.837955 0.505252 -0.426092 C -0.505711 0.790645 -0.681171 B 1.249441 -0.386199 2.587609 C 2.033518 0.802068 3.201051 C 3.355208 0.726322 3.717599 C 3.823130 1.759412 4.541146 C 3.030642 2.864024 4.817183 C 1.764540 2.989083 4.262927 C 1.293379 1.967320 3.453548 N 4.169340 -0.359533 3.405622 C 5.394617 -0.559394 4.146523 F -1.614584 -0.880605 2.885025 F -3.483140 -0.327666 1.031617 F -2.761315 0.771097 -1.340892 F -0.153649 1.323629 -1.846826 F 1.720462 0.787628 0.003485 C 4.258862 -0.827872 2.032496 C 1.393645 -1.880828 3.053113 C 1.241806 -2.950747 1.963408




120

H 4.208463 -1.920453 1.988058 H 5.755570 -1.572286 3.954416 H 6.192735 0.144118 3.859024 H 5.213333 -0.467818 5.218575 H 3.450341 -0.418941 1.428742 H 5.205379 -0.505948 1.574745 H 4.825186 1.723136 4.947648 H 3.425671 3.649452 5.452706 H 1.156348 3.863364 4.459912 H 0.295507 2.049343 3.033836 H 2.015527 -2.851186 1.196131 H 1.319819 -3.957591 2.380737 H 0.274086 -2.875735 1.460302 H 0.569353 -2.000358 3.774708 H 2.311497 -2.030513 3.624296 38 int C -1.133077 0.347691 1.767999 C 0.167125 0.025404 1.407788 C 0.607404 0.579768 0.214255 C -0.160453 1.421110 -0.571472 C -1.452052 1.721857 -0.167515 C -1.943985 1.179308 1.007494 B 1.084349 -1.009335 2.242511 C 1.345079 -2.384873 1.451448 F 1.856841 0.316782 -0.221186 F 0.321244 1.939583 -1.699316 F -2.212346 2.523933 -0.904984 F -3.187032 1.457677 1.392914 F -1.674844 -0.160777 2.881014 C 0.934942 -1.152304 3.838704 C 2.185976 -0.624532 4.075155 C 2.804988 -0.527340 5.306186 C 2.063643 -1.014540 6.381273 C 0.788305 -1.550257 6.188948 C 0.208169 -1.626128 4.923184 N 2.613152 -0.217106 2.734330 C 3.870477 -0.826442 2.270708 C 2.677980 1.252278 2.611042 H 2.877480 1.518222 1.573668 H 3.973293 -0.643691 1.200721 H 4.722335 -0.391407 2.802085 H 3.842243 -1.898175 2.452797 H 1.725644 1.678822 2.922224 H 3.475118 1.644275 3.249369 H 3.794083 -0.104766 5.444202 H 2.480242 -0.973915 7.381158 H 0.239695 -1.914340 7.050946 H -0.786723 -2.039480 4.802636 H 2.021920 -3.036418 2.016754 C 0.023059 -3.136594 1.244747 H 1.816118 -2.205594 0.477692 H 0.175960 -4.098162 0.747385 H -0.469701 -3.334324 2.202125 H -0.673953 -2.556140 0.632585 40 TSsplit

C 2.889900 -1.582500 0.021800 C 2.047400 -0.494900 -0.230200 C 2.357700 0.727700 0.384900 C 3.471100 0.843800 1.213200




121

C 4.284200 -0.254500 1.456000 C 3.991200 -1.473600 0.859600 B 0.782200 -0.679100 -1.168400 C 0.822900 -1.718700 -2.364800 N 1.510200 1.859600 0.113000 C 2.223100 3.045100 -0.340500 C -0.659200 -0.374400 -0.524200 C -1.058600 -1.212400 0.508800 C -2.254100 -1.064400 1.192300 C -3.109400 -0.034500 0.835500 C -2.759100 0.814600 -0.200800 C -1.558000 0.624500 -0.867500 F -0.261000 -2.224600 0.879400 F -1.286200 1.484100 -1.858200 F -3.576700 1.805000 -0.548700 F -4.260600 0.131200 1.476000 F -2.587500 -1.895300 2.175200 C 0.598500 2.166000 1.208700 H 1.497700 3.773100 -0.713300 H -0.158700 2.875600 0.862800 H 1.118700 2.604500 2.075700 H 0.094400 1.256700 1.537500 H 2.896000 2.778300 -1.158100 H 2.814600 3.531800 0.451200 H 3.701200 1.797500 1.676300 H 5.144400 -0.157300 2.109000 H 4.622200 -2.336000 1.042200 H 2.675700 -2.539500 -0.442300 H 1.014400 1.073700 -1.770800 H 1.016500 0.638300 -2.401900 C -0.285900 -1.597600 -3.413200 H 0.737600 -2.698600 -1.869800 H 1.808800 -1.721400 -2.842400 H -0.215500 -2.385000 -4.167400 H -0.237300 -0.636800 -3.935700 H -1.275500 -1.664900 -2.952700 40 intH2

C 2.461100 -1.864100 0.225200 C 1.933400 -0.637900 -0.199500 C 2.501600 0.479300 0.407000 C 3.506000 0.445600 1.363500 C 3.992500 -0.791900 1.755400 C 3.466000 -1.944700 1.179200 B 0.745900 -0.476900 -1.312000 C 0.666500 -1.692600 -2.381700 N 1.949700 1.781600 -0.030700 C 2.960200 2.685000 -0.630400 C -0.686600 -0.232900 -0.534100 C -1.286300 -1.232200 0.224300 C -2.507500 -1.084300 0.863500 C -3.184100 0.121900 0.769000 C -2.624100 1.155500 0.039500 C -1.404900 0.952000 -0.590000 F -0.678900 -2.418500 0.370600 F -0.903400 2.025000 -1.250900 F -3.251100 2.330800 -0.041800 F -4.353600 0.287300 1.382600 F -3.035800 -2.080600 1.572800 C 1.131000 2.443800 1.015100 H 2.452100 3.560400 -1.034900 H 0.607700 3.290600 0.572900




122

H 1.784000 2.772800 1.823100 H 0.411800 1.718200 1.389700 H 3.467500 2.143400 -1.426800 H 3.679200 2.988200 0.129300 H 3.904900 1.354300 1.803100 H 4.774500 -0.855500 2.502400 H 3.844600 -2.914800 1.481700 H 2.063700 -2.775700 -0.205900 H 1.323700 1.485600 -0.818200 H 0.977600 0.555600 -1.966100 C -0.387200 -1.473200 -3.470300 H 0.460300 -2.646600 -1.880600 H 1.651000 -1.810700 -2.854200 H -0.412300 -2.289200 -4.199800 H -0.197500 -0.543200 -4.016900 H -1.390300 -1.391300 -3.037400 40 TSprot

C 0.020800 -0.053300 -0.005800 C 0.029300 -0.040400 -1.403200 C -1.101000 0.487600 -2.025000 C -2.186100 1.001000 -1.328000 C -2.161500 0.972300 0.059500 C -1.057900 0.439500 0.716900 B 1.223600 -0.614800 -2.314900 C 1.624500 0.493400 -3.852600 N -1.036800 0.453600 -3.472100 C -1.450300 1.691800 -4.134800 C 2.609700 -0.739700 -1.494600 C 3.240700 0.365100 -0.935300 C 4.400900 0.283100 -0.184600 C 4.973200 -0.960800 0.033400 C 4.379200 -2.091300 -0.501100 C 3.217200 -1.963600 -1.251200 F 2.720700 1.587500 -1.127200 F 2.690300 -3.093900 -1.733800 F 4.928400 -3.286500 -0.291500 F 6.087200 -1.065900 0.751300 F 4.969600 1.373700 0.326700 C -1.706800 -0.730100 -4.031300 H -1.175300 1.638900 -5.190100 H -1.509500 -0.786600 -5.103200 H -2.788400 -0.677200 -3.862900 H -1.309000 -1.621800 -3.549200 H -0.934000 2.533500 -3.672800 H -2.531400 1.853000 -4.063800 H -3.043300 1.411300 -1.851000 H -3.000400 1.362100 0.624300 H -1.036700 0.416100 1.800800 H 0.876400 -0.453600 0.528300 H 0.359200 0.314200 -3.517600 H 0.941500 -1.643200 -2.875000 C 1.548300 -0.084300 -5.269000 H 2.640200 0.359800 -3.493400 H 1.492700 1.583100 -3.841300 H 2.329400 0.330700 -5.910400 H 0.588600 0.124900 -5.750800 H 1.673800 -1.169100 -5.241100


supplementary information - nature · 2013-07-23 · 1-methyl-4-prop-1-ynylbenzene-d. 3 (26a) 55...

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