Nickel-Mediated Stepwise Transformation of CO to Acetaldehyde and Ethanol Ailing Zhang, Sakthi Raje, Jianguo Liu, Xiaoyan Li, Raja Angamuthu, Chen-Ho Tung, and Wenguang Wang* School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China Laboratory of Inorganic Synthesis and Bioinspired Catalysis (LISBIC), Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India Figure S1. 1 H NMR spectrum of [1](BF 4 ) 2... p S2 Figure S2. 31 P { 1 H} NMR spectrum of [1](BF 4 ) 2... p S3 Figure S3. ESI-MS spectrum of [1](BF 4 ) 2... p S4 Figure S4. ESI-MS spectrum of [1(NCMe) 2 ](BF 4 ) 2... p S5 Figure S5. 1 H NMR spectrum of [1-H]BF 4... p S6 Figure S6. 31 P { 1 H} NMR spectrum of [1-H]BF 4... p S7 Figure S7. ESI-MS spectrum of [1-H]BF 4... p S8 Figure S8. Crystal structure of [1-H]BF 4... p S9 Figure S9. 1 H NMR spectrum of [1] 0... p S10 Figure S10. 31 P { 1 H} NMR spectrum of [1] 0... p S11 Figure S11. 1 H NMR spectrum of [1-CH 3 ]BPh 4... p S12 Figure S12. 31 P { 1 H} NMR spectrum of [1-CH 3 ]BPh 4... p S13 Figure S13. 13 C NMR spectrum of [1-CH 3 ]BPh 4... p S14 Figure S14. ESI-MS spectrum of [1-CH 3 ]BPh 4... p S15 Figure S15. 2 H NMR spectrum of [1-CD 3 ]BPh 4... p S16 Figure S16. 31 P { 1 H} NMR spectrum of [1-CD 3 ]BPh 4... p S17 Figure S17. ESI-MS spectrum of [1-CD 3 ]BPh 4... p S18 Figure S18. 1 H NMR spectrum of [1-COCH 3 ]BPh 4... p S19 Figure S19. 31 P { 1 H} NMR spectrum of [1-COCH 3 ]BPh 4... p S20 Figure S20. 13 C NMR spectrum of [1-COCH 3 ]BPh 4... p S21 Figure S21. ESI-MS spectrum of [1-COCH 3 ]BPh 4... p S22 Figure S22. 2 H NMR spectrum of [1-COCD 3 ]BPh 4... p S23 Figure S23. 31 P { 1 H} NMR spectrum of [1-COCD 3 ]BPh 4... p S24 Figure S24. 13 C NMR spectrum of [1-COCD 3 ]BPh 4... p S25 Figure S25. ESI-MS spectrum of [1-COCD 3 ]BPh 4... p S26 Figure S26. IR spectra of [1-COCD 3 ]BPh 4 and [1-COCH 3 ]BPh 4... p S27 Figure S27. IR spectra recorded for the reaction of [1-COCH 3 ]BPh 4 and NBu 4 BH 4... p S28 Figure S28. 2 H NMR spectra of CD 3 CHO and CD 3 CH 2 OH... p S29 Figure S29. 1 H NMR spectrum of [1-CO] 0... p S30 Figure S30. 31 P { 1 H} NMR spectrum of [1-CO] 0... p S31 Table S1-S6. Crystal data and structure refinement parameters p S32-S38 S1
Figure S1. 1 H NMR spectrum of [1](BF 4 ) 2 in CD 2 Cl 2. S2
Figure S2. 31 P NMR spectrum of [1](BF 4 ) 2 in CD 2 Cl 2. S3
Figure S3. ESI-MS spectrum of [1](BF 4 ) 2. S4
Figure S4. ESI-MS spectrum of [1(NCMe) 2 ](BF 4 ) 2. S5
Figure S5. 1 H NMR spectrum of [1-H]BF 4 in CD 3 CN. S6
Figure S6. 31 P NMR spectrum of ([1-H]BF 4 in CD 3 CN. S7
Figure S7. ESI-MS spectrum for [1-H]BF 4. S8
Figure S8. Molecular Structure (50% probability thermal ellipsoids) of [1-H]BF 4. For clarity, the BF 4 - counter anions are not shown and hydrogen atoms except for the hydride ligand are omitted. Selected distances (Å) and angles (deg): [1-H] +, Ni1-S 2.2532(9), 2.339(1), Ni1-P 2.139(1), 2.146(1), S1-Ni1-S2 90.63(4), P1-Ni1-S1 97.29(4), P1-Ni1-S2 107.20(4), P1-Ni1-P2 152.62(4), P2-Ni1-S1 99.60(3), P2-Ni1-S2 94.04(4). S9
Figure S9. 1 H NMR spectrum of [1] 0 in C 6 D 6. S10
Figure S10. 31 P NMR spectrum of [1] 0 in C 6 D 6. S11
Figure S11. 1 H NMR spectrum of [1-CH 3 ]BPh 4 in CD 2 Cl 2. S12
Figure S12. 31 P NMR spectrum of [1-CH 3 ]BPh 4 in CD 2 Cl 2. S13
Figure S13. 13 C NMR spectrum of [1-CH 3 ]BPh 4 in CD 2 Cl 2. S14
Figure S14. ESI-MS spectrum of [1-CH 3 ]BPh 4. S15
Figure S15. 2 H NMR spectrum of [1-CD 3 ]BPh 4 in CH 2 Cl 2. S16
Figure S16. 31 P NMR spectrum of [1-CD 3 ]BPh 4 in CD 2 Cl 2. S17
Figure S17. ESI-MS spectrum of [1-CD 3 ]BPh 4. S18
Figure S18. 1 H NMR spectrum of [1-COCH 3 ]BPh 4 in CD 2 Cl 2. S19
Figure S19. 31 P NMR spectrum of [1-COCH 3 ]BPh 4 in CD 2 Cl 2. S20
Figure S20. 13 C NMR spectrum of [1-COCH 3 ]BPh 4 in CD 2 Cl 2. S21
Figure S21. ESI-MS spectrum of [1-COCH 3 ]BPh 4. S22
Figure S22. 2 H NMR spectrum of [1-COCD 3 ]BPh 4 in CH 2 Cl 2. S23
Figure S23. 31 P NMR spectrum of [1-COCD 3 ]BPh 4 in CD 2 Cl 2. S24
Figure S24. 13 C NMR spectrum of [1-COCD 3 ]BPh 4 in CD 2 Cl 2. S25
Figure S25. ESI-MS spectrum of [1-COCD 3 ]BPh 4. S26
Figure S26. IR spectra (ν CO region) of [1-COCH 3 ]BPh 4 and [1-COCD 3 ]BPh 4 in CH 2 Cl 2 solution. Result: [1-COCD 3 ]BPh 4, ν CO (cm -1, CH 2 Cl 2 ), 1660. [1-COCH 3 ]BPh 4, ν CO (cm -1, CH 2 Cl 2 ), 1663. S27
Figure S27. IR spectra for (a) [1-COCH 3 ]BPh 4 in MeCN solution, (b) the reaction of [1-COCH 3 ]BPh 4 and NBu 4 BH 4 in MeCN solution. Results: a) ν CO (cm -1, CH 3 CN), 1660. b) ν CO (cm -1, CH 3 CN), 1907, 1724. S28
Figure S28. 2 H NMR spectra of CD 3 CHO and CD 3 CH 2 OH produced by the reaction of [1-COCH 3 ]BPh 4 with two equiv of NBu 4 BH 4 in THF. Note: 1 µl of H 2 O was added to the mixture to quench the reaction before conducting NMR analysis S29
Figure S29. 1 H NMR spectrum of [1-CO] 0 in CD 3 CN. S30
Figure S30. 31 P NMR spectrum of [1-CO] 0 in CD 3 CN. S31
X-ray Crystallography Single crystals with appropriate dimensions were chosen under an optical microscope and quickly coated with high vacuum grease (Dow Corning Corporation) to prevent decomposition. Intensity data and cell parameters were recorded at 173 K on a Bruker Apex II single crystal diffractometer, employing a Mo K α radiation (λ = 0.71073 Å) and a CCD area detector. The raw frame data were processed using SAINT and SADABS to yield the reflection data file. 1 The structure was solved using the charge-flipping algorithm, as implemented in the program SUPERFLIP 2 and refined by full-matrix least-squares techniques against F 2 o using the SHELXL program 3 through the OLEX2 interface. 4 Hydrogen atoms at carbon were placed in calculated positions and refined isotropically by using a riding model. Appropriate restraints or constraints were applied to the geometry and the atomic displacement parameters of the atoms in the cluster. All structures were examined using the Addsym subroutine of PLATON 5 to ensure that no additional symmetry could be applied to the models. Pertinent crystallographic data collection and refinement parameters are collated in Table S1-S6. Reference: 1. APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA, 2015. 2. Palatinus, L.; Chapuis, G. J. Appl. Cryst. 2007, 40, 786 790. 3. Sheldrick, G. M. Acta. Cryst. Sect. C 2015, 71, 3 8. 4. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Cryst. 2009, 42, 339 341. 5. Spek, A. L. Acta Cryst. Sect. D 2009, 65, 148 155. S32
Table S1: Crystal data and structure refinement parameters for [1](BF 4 ) 2 Empirical formula C 40 H 36 B 2 F 8 NiP 2 S 2 Formula weight 875.08 Crystal system monoclinic Space group P 2 1 /c Unit cell dimensions a = 9.106(3) Å b = 19.828(7) Å c = 21.472(7) Å α = 90 β = 99.903(3) γ = 90 Volume 3819(2) Å 3 Z 4 Density (calculated) 1.522 g/cm 3 Absorption coefficient 0.771 mm -1 F(000) 1792 Crystal size 0.1 0.09 0.08 mm 3 Theta range for data collection 4.98 to 50 Index ranges -10 h 10, -23 k 23, -18 l 25 Reflections collected 20010 Independent reflections 6731 [R(int) = 0.0809] Completeness to theta = 50 89.3 % Absorption correction multi-scan Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6731/0/496 Goodness-of-fit on F 2 1.019 Final R indices [I>2sigma(I)] R 1 = 0.0507, wr 2 = 0.0837 R indices (all data) R 1 = 0.1004, wr 2 = 0.0988 Largest diff. peak and hole 0.748 and -0.563 e.å -3 S33
Table S2: Crystal data and structure refinement parameters for [1(NCMe) 2 ](BF 4 ) 2 Empirical formula C 26 H 31 BF 4 NNi 0.50 OPS Formula weight 552.71 Crystal system monoclinic Space group C 2/c Unit cell dimensions a = 28.649(4) Å b = 12.5692(15) Å c = 19.399(2) Å α = 90 β = 124.8285(10) γ = 90 Volume 5734.0(12) Å 3 Z 8 Density (calculated) 1.281 g/cm 3 Absorption coefficient 0.532 mm -1 F(000) 2304.0 Crystal size 0.12 0.10 0.09 mm 3 Theta range for data collection 5.368 to 49.996 Index ranges -34 h 34, -14 k 14, -23 l 23 Reflections collected 19093 Independent reflections 5044 [R(int) = 0.0266] Completeness to theta = 50 88.5 % Absorption correction multi-scan Max. and min. transmission 0.7456 and 0.7076 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5044/0/324 Goodness-of-fit on F2 1.103 Final R indices [I>2sigma(I)] R 1 = 0.0539, wr 2 = 0.1580 R indices (all data) R 1 = 0.0677, wr 2 = 0.1676 Largest diff. peak and hole 1.028 and -0.521 e.å -3 S34
Table S3: Crystal data and structure refinement parameters for [1-H]BF 4 Empirical formula C 40 H 37 BF 4 NiP 2 S 2 Formula weight 789.28 Crystal system triclinic Space group P -1 Unit cell dimensions a = 11.2710(8) Å b = 14.4906(11) Å c = 15.8999(12) Å α = 100.947(4) β = 108.989(4)(10) γ = 110.958(4) Volume 2150.7(3) Å 3 Z 2 Density (calculated) 1.219 g/cm 3 Absorption coefficient 0.665 mm -1 F(000) 816.0 Crystal size 0.15 0.08 0.04 mm 3 Theta range for data collection 5.52 to 49.98 Index ranges -13 h 13, -17 k 17, -18 l 18 Reflections collected 16011 Independent reflections 7328 [R(int) = 0.0444] Completeness to theta = 50 89.0 % Absorption correction multi-scan Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7328/0/455 Goodness-of-fit on F2 0.952 Final R indices [I>2sigma(I)] R 1 = 0.0453, wr 2 = 0.1091 R indices (all data) R 1 = 0.0693, wr 2 = 0.1191 Largest diff. peak and hole 0.453 and -0.334 e.å -3 S35
Table S4: Crystal data and structure refinement parameters for [1-CH 3 ] BPh 4 Empirical formula C 66 H 61 BCl 2 NiP 2 S 2 Formula weight 1120.62 Crystal system triclinic Space group P -1 Unit cell dimensions a = 9.9999(7) Å b = 15.3446(11) Å c = 20.6266(15) Å α = 96.893(5) β = 102.757(5) γ = 99.711(5) Volume 3001.7(4) Å 3 Z 2 Density (calculated) 1.240 g/cm 3 Absorption coefficient 0.574 mm -1 F(000) 1172.0 Crystal size 0.16 0.11 0.08 mm 3 Theta range for data collection 5.134 to 49.998 Index ranges -11 h 11, -18 k 18, 0 l 24 Reflections collected 31775 Independent reflections 10523 [R(int) = 0.0551] Completeness to theta = 50 89.0 % Absorption correction multi-scan Max. and min. transmission 0.7456 and 0.6448 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 10523/0/668 Goodness-of-fit on F2 1.060 Final R indices [I>2sigma(I)] R 1 = 0.0648, wr 2 = 0.1693 R indices (all data) R 1 = 0.0930, wr 2 = 0.1820 Largest diff. peak and hole 1.480 and -0.925 e.å -3 S36
Table S5: Crystal data and structure refinement parameters for [1-COCH 3 ]BPh 4 Empirical formula C 66 H 59 BNiOP 2 S 2 Formula weight 1016.50 Crystal system monoclinic Space group P 2 1 /c Unit cell dimensions a = 15.179(5) Å b = 14.611(5) Å c = 27.455(9) Å α = 90 β = 98.192(3) γ = 90 Volume 6027(3) Å 3 Z 4 Density (calculated) 1.172 g/cm 3 Absorption coefficient 0.482 mm -1 F(000) 2021.0 Crystal size 0.09 0.07 0.05 mm 3 Theta range for data collection 5.14 to 50 Index ranges -17 h 18, -17 k 17, -32 l 32 Reflections collected 42307 Independent reflections 10517 [R(int) = 0.1079] Completeness to theta = 50 89.7 % Absorption correction multi-scan Max. and min. transmission 0.7456 and 0.6774 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 10517/0/659 Goodness-of-fit on F2 0.908 Final R indices [I>2sigma(I)] R 1 = 0.0560, wr 2 = 0.1015 R indices (all data) R 1 = 0.1157, wr 2 = 0.1177 Largest diff. peak and hole 0.388 and -0.487 e.å -3 S37
Table S6: Crystal data and structure refinement parameters for [1-CO] 0 Empirical formula C 41 H 36 NiOP 2 S 2 Formula weight 729.47 Crystal system triclinic Space group P -1 Unit cell dimensions a = 12.300(5) Å b = 12.430(5) Å c = 12.787(5) Å α = 83.091(3) β = 64.890(3) γ = 82.627(3) Volume 1750.8(12) Å 3 Z 2 Density (calculated) 1.384 g/cm 3 Absorption coefficient 0.797 mm -1 F(000) 760.0 Crystal size 0.13 0.09 0.06 mm 3 Theta range for data collection 3.66 to 50 Index ranges -14 h 14, -14 k 14, -15 l 15 Reflections collected 20719 Independent reflections 6179 [R(int) = 0.0359] Completeness to theta = 50 92.7 % Absorption correction multi-scan Max. and min. transmission 0.7456 and 0.6661 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6179/0/424 Goodness-of-fit on F2 1.056 Final R indices [I>2sigma(I)] R 1 = 0.0266, wr 2 = 0.0651 R indices (all data) R 1 = 0.0332, wr 2 = 0.0700 Largest diff. peak and hole 0.350 and -0.261 e.å -3 S38