Supporting Information for: Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX 3 Compounds Michael T. Mock, Robert G. Potter, Molly J. O Hagan, Donald M. Camaioni, William G. Dougherty, W. Scott Kassel, and Daniel L. DuBois* Pacific Northwest National Laboratory, Richland, Washington 99352 Department of Chemistry, Villanova University, Villanova, Pennsylvania 19085 Table of Contents Experimental details for cyclic voltammetry S-2 Figure S1. Cyclic voltammogram of [Co(dmpe) 2 (CH 3 CN) 2 ][BF 4 ] 2 S-2 Figure S2. Cyclic voltammogram of [Co(dedpe) 2 (CH 3 CN)][BF 4 ] 2 S-3 Figure S3. Molecular structure of Co(dmpe) 2 (SPh) HSPh S-3 Figure S4. Molecular structure of [Ni(dmpe) 2 (SPh)][B(Ph) 4 ] S-4 X-ray Crystallographic details of Co(dmpe) 2 (SPh)-HSPh and [Ni(dmpe) 2 (SPh)][B(Ph) 4 ] S-4 X-ray Crystallographic data for Co(dmpe) 2 (SPh)-HSPh and S-5 [Ni(dmpe) 2 (SPh)][B(Ph) 4 ] Complete Reference 33 S-6 Figure S5. 31 P NMR spectrum recorded at -40 C in CD 3 CN of the reactionbetween [Co(dedpe) 2 (CH 3 CN)][BF 4 ] and H 2. S-6 Figure S6. 31 P-coupled 1 H NMR spectrum recorded at -40 C in CD 3 CN showing the hydride region of the reaction between [Co(dedpe) 2 (CH 3 CN)][BF 4 ] and H 2. S-7 Table 1S. Energies (a.u.) and entropies (cal mol -1 K -1 ) of species calculated at B3LYP/DZVP2 level of theory. S-8 Table 2S. Energies (a.u.) calculated at B3LYP/aug-cc-pVTZ//B3LYP/DZVP2 level of theory. S-9 Table 3S. Energies at 298 K for hydride transfer from BH 4 to BX 3 calculated at B3LYP/DZVP2 and B3LYP/aug-cc-pVTZ//B3LYP/DZVP2 levels of theory. S-10 Table 4S. Hydride affinities of BX 3 species calculated from energies in Table 3S. S-10 Cartesian coordinates of structures optimized at B3LYP/DZVP2 level of theory S-11 S -1
Experimental details for cyclic voltammetry. Cyclic voltammetry was performed in a Vacuum Atmospheres Nexus II glovebox under an N 2 atmosphere using a CH Instruments model 660C potentiostat. A typical three-electrode single compartment electrochemical cell was used; that included a glassy carbon working electrode, a Ag + /Ag pseudoreference electrode and a glassy carbon rod as auxiliary electrode in THF or acetonitrile with 0.10 M tetraethylammonium tetrafluoroborate or tetrabutylammonium tetrafluoroborate as the supporting electrolyte. Ferrocene or decamethylferrocene was used as an internal reference with all potentials reported versus the ferrocene/ferrocenium couple. Figure S1. Cyclic voltammogram of [Co(dmpe) 2 (CH 3 CN) 2 ] 2+ in acetonitrile. E 1/2 = -1.20 V (Co II/I ). S -2
Figure S2. Cyclic voltammogram of [Co(dedpe) 2 (CH 3 CN)] 2+ in acetonitrile. E 1/2 = -0.95 V (Co II/I ); -1.91 V (Co I/0 ); -2.25 V (Co 0/-1 ). Figure S3. Molecular structure of Co(dmpe) 2 (SPh) HSPh. Thermal ellipsoids drawn at 30% probability. Hydrogen atoms omitted. S -3
Figure S4. Molecular structure of [Ni(dmpe) 2 (SPh)][B(Ph) 4 ]. Thermal ellipsoids drawn at 30% probability. Hydrogen atoms omitted. X-Ray Crystallographic Details of [Ni(dmpe) 2 (SPh)][B(Ph) 4 ]: A single red block (0.12 X 0.15 X 0.20 mm) was mounted using NVH immersion oil onto a nylon fiber and cooled to the data collection temperature of 100(2) K. Data were collected on a Brüker- AXS Kappa APEX II CCD diffractometer with 0.71073 Å Mo-Kα radiation. Unit cell parameters were obtained from 90 data frames, 0.3º Φ, from three different sections of the Ewald sphere yielding a = 12.0642(3) Å, b = 10.0238(3) Å, c = 33.641(1) Å, β = 92.516(1), V = 4064.2(2) Å 3. 34748 reflections (R int = 0.0401) were collected (15442 unique) over θ = 2.12 to 33.36. The systematic absences in the diffraction data were consistent with the centrosymmetric, monoclinic space group, P2 1 /c. The data-set was treated with SADABS absorption corrections based on redundant multi-scan data (Sheldrick, G,.Bruker-AXS, 2001) T max /T min = 1.06. The cation and anion were located on general positions yielding Z = 4, and Z = 1. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were treated as idealized contributions. The goodness of fit on F 2 was 1.067 with R1(wR2) 0.0656(0.1274) for [Iθ>2(I)] and with largest difference peak and hole of 1.559 and 0.808 e/å 3. X-Ray Crystallographic Details of Co(dmpe) 2 (SPh) HSPh: A single orange block (0.20 X 0.21 X 0.25 mm) was mounted using Paratone oil onto a glass fiber and cooled to the data collection temperature of 100(2) K. Data were collected on a Brüker-AXS Kappa APEX II CCD diffractometer with 1.54178 Å Cu-Kα radiation. Unit cell parameters were obtained from 90 data frames, 0.3º Φ, from three different sections of the Ewald sphere yielding a = 9.691(1), b = 11.974(1), c = 24.414(1) Å, β = 96.651(1), V = S -4
2813.8(1) Å 3. 14531 reflections (R int = 0.0286) were collected (5076 unique) over θ = 3.65 to 68.37. The systematic absences in the diffraction data were consistent with the centrosymmetric, monoclinic space group, P2(1)/n. The data-set was treated with SADABS absorption corrections based on redundant multi-scan data (Sheldrick, G,.Bruker-AXS, 2001) T max /T min = 1.24. The asymmetric unit contains one (dmpe) 2 Co(SPh) and one molecule of thiophenol both located on general positions, yielding Z = 4, and Z = 1. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were treated as idealized contributions except the proton on the thiophenol which was located from the difference map and allowed to refine freely. The goodness of fit on F 2 was 1.041 with R1(wR2) 0.0370(0.0923) for [Iθ>2(I)] and with largest difference peak and hole of 0.780 and 0.542 e/å 3. Crystallographic data for [Ni(dmpe) 2 (SPh)][B(C 6 H 5 ) 4 ], Co(dmpe) 2 (SPh) HSPh. [Ni(dmpe) 2 (SPh)] [B(C 6 H 5 ) 4 ] Co(dmpe) 2 (SPh) HSPh empirical formula C 42 H 57 BNiP 4 S C 24 H 43 CoP 4 S 2 formula weight 787.34 578.51 color, habit red, blocks orange, blocks crystal system monoclinic monoclinic space group P2(1)/c P2(1)/n a, Å 12.0642(3) 9.6910(2) b, Å 10.0238(3) 11.9736(2) c, Å 33.6406(9) 24.4141(5) α, deg 90 90 β, deg 92.5160(10) 96.6510(10) γ, deg 90 90 V(Å 3 ) 4064.21(19) 2813.85(9) λ, Å (Cu (Mo), Kα) (0.71073) 1.54178 Z 4 4 density (g/cm 3 ) 1.287 1.366 temperature (K) 100(2) 100(2) 2θ range, deg 2.12 33.36 3.65 68.73 µ(cu (Mo), Kα), mm -1 (0.715) 8.394 R(F), Rw(F) 0.0656, 0.1274 0.0353, 0.0910 Quantity minimized = R(wF 2 ) = Σ[w(F o 2 F c 2 ) 2 ]/ Σ[(wF o 2 ) 2 ] 1/2 ; R = Σ /Σ(F o ), = (F o F c ), w = 1/[σ 2 (F o 2 ) + (ap) 2 + bp], P = [2F c 2 + Max(F o,0)]/3 S -5
Full citation for reference 33. E. J. Bylaska, W. A. de Jong, N. Govind, K. Kowalski, T. P. Straatsma, M. Valiev, D. Wang, E. Apra, T. L. Windus, J. Hammond, P. Nichols, S. Hirata, M. T. Hackler, Y. Zhao, P.-D. Fan, R. J. Harrison, M. Dupuis, D. M. A. Smith, J. Nieplocha, V. Tipparaju, M. Krishnan, A. Vazquez-Mayagoitia, Q. Wu, T. Van Voorhis, A. A. Auer, M. Nooijen, L. D. Crosby, E. Brown, G. Cisneros, G. I. Fann, H. Fruchtl, J. Garza, K. Hirao, R. Kendall, J. A. Nichols, K. TsemekhmanK. Wolinski, J. Anchell, D. Bernholdt, P. Borowski, T. Clark, D. Clerc, H. Dachsel, M. Deegan, K. Dyall, D. Elwood, E. Glendening M. Gutowski, A. Hess, J. Jaffe, B. Johnson, J. Ju, R. Kobayashi, R. Kutteh, Z. Lin, R. Littlefield, X. Long, B. Meng, T. Nakajima, S. Niu, L. Pollack, M. Rosing, G. Sandrone, M. Stave, H. Taylor, G. Thomas, J. van Lenthe, A. Wong, and Z. Zhang, "NWChem, A Computational Chemistry Package for Parallel Computers, Version 5.1.1" (2009), Pacific Northwest National Laboratory, Richland, Washington 99352-0999, USA. Figure S5. 31 P NMR spectrum recorded at -40 C in CD 3 CN of the reaction between [Co(dedpe) 2 (CH 3 CN)][BF 4 ] and H 2. Inset is the 31 P NMR spectrum recorded at 21 C. S -6
Figure S6. 31 P-coupled 1 H NMR spectrum recorded at -40 C in CD 3 CN showing the hydride region of the reaction between [Co(dedpe) 2 (CH 3 CN)][BF 4 ] and H 2. Inset is the corresponding 1 H{ 31 P} NMR spectrum. S -7
Table 1S. Energies (a.u.) and entropies (cal mol -1 K -1 ) of species calculated at B3LYP/DZVP2 level of theory. Species Electronic E Zero Point E E298-E S 298 E 298 BH 3-26.61856 0.02610 0.02899 44.99900-26.58957 BH 4-27.26716 0.03335 0.03726 45.25800-27.22990 BEt 3-262.61461 0.19939 0.21007 99.03800-262.40454 BHEt 3-263.23656 0.20614 0.21677 97.24100-263.01978 BF 3-324.67361 0.01221 0.01574 60.97200-324.65787 BHF 3-325.33072 0.02010 0.02392 63.58300-325.30680 BH 2 SPh -655.96462 0.11307 0.12049 85.82600-655.84413 BH 3 SPh -656.62303 0.12003 0.12793 87.17700-656.49510 B(OPh) 3-945.82496 0.28965 0.30768 70.83100-945.51728 BH(OPh) 3-946.47831 0.29711 0.31524 138.80700-946.16307 BH(SPh) 2-1285.29309 0.19721 0.21083 120.39600-1285.08226 BH 2 (SPh) 2-1285.95784 0.20467 0.21871 120.89100-1285.73913 B(SPh) 3-1914.61372 0.28083 0.30082 150.26800-1914.31290 BH(SPh) 3-1915.28886 0.28837 0.30869 150.07600-1914.98017 B(OC 6 F 5 ) 3-2434.78098 0.17189 0.20087 176.07300-2434.58010 BH(OC 6 F 5 ) 3-2435.47162 0.17881 0.20843 178.16200-2435.26319 S -8
Table 2S. Energies (a.u.) calculated at B3LYP/aug-cc-pVTZ//B3LYP/DZVP2 level of theory. Species Electronic E BH 3-26.62434 BH 4-27.27890 BEt 3-262.64340 BHEt 3-263.27243 BF 3-324.70078 BHF 3-325.35280 BH 2 SPh -656.03370 BH 3 SPh -656.69485 B(OPh) 3-945.96019 BH(OPh) 3-946.61298 BH(SPh) 2-1285.42557 BH 2 (SPh) 2-1286.09113 B(SPh) 3-1914.80931 BH(SPh) 3-1915.48405 B(OC 6 F 5 ) 3-2434.98135 BH(OC 6 F 5 ) 3-2435.66646 S -9
Table 3S. Energies at 298 K for hydride transfer from BH 4 to BX 3 calculated at B3LYP/DZVP2 and B3LYP/aug-cc-pVTZ//B3LYP/DZVP2 levels of theory. BX 3 DZVP2 aug-cc-pvtz a BEt 3 15.7 15.0 BF 3-5.4 1.5 B(OPh) 3-3.4 0.7 BH 2 SPh -6.7-4.6 BH(SPh) 2-10.4-7.1 B(SPh) 3-16.9-12.9 B(OC 6 F 5 ) 3-26.8-19.6 a Corrected to 298 K using E298-E calculated for DZVP2 basis. Table 4S. Hydride affinities of BX 3 species calculated from energies in Table 3S and assuming HA (BH 3 ) = 73.7 kcal/mol. 1 BX 3 DZVP2 aug-cc-pvtz BEt 3 58.0 58.7 BF 3 79.1 72.2 B(OPh) 3 77.1 73.0 BH 2 SPh 80.4 78.3 BH(SPh) 2 84.1 80.8 B(SPh) 3 90.6 86.6 B(OC 6 F 5 ) 3 100.5 93.3 1 Grant, D. J.; Dixon, D. A.; Camaioni, D.; Potter, R. G.; Christe, K. O. Inorg. Chem. 2009, 48, 8811. S -10
Cartesian coordinates of structures optimized at B3LYP/DZVP2 level of theory BH 3 B 0.00000000 0.00000000 0.00000000 H 0.84386569 0.84386569 0.00000000 H 0.30887628-1.15274197 0.00000000 H -1.15274197 0.30887628 0.00000000 BH 4 B 0.00000000 0.00000000 0.00000000 H -0.71500376 0.71500376 0.71500376 H 0.71500376-0.71500376 0.71500376 H -0.71500376-0.71500376-0.71500376 H 0.71500376 0.71500376-0.71500376 BEt 3 B 0.00000000 0.00000000 0.00000000 C 2.69674608 0.00000000 0.00000000 C 1.37521386 0.78872436 0.00000000 C -0.00455160-1.58533231 0.00000000 C -1.34837304-2.33545061 0.00000000 C -1.37066226 0.79660796 0.00000000 C -1.34837304 2.33545061 0.00000000 H 3.56574760 0.66780243 0.00000000 H -2.36120767 2.75412679 0.00000000 H -1.20453993-3.42192922 0.00000000 H 2.78174760-0.64545166 0.88127107 H -0.83189627 2.73178992 0.88127107 H -1.94985134-2.08633826 0.88127107 H 2.78174760-0.64545166-0.88127107 H -0.83189627 2.73178992-0.88127107 H -1.94985134-2.08633826-0.88127107 H 1.35340284 1.47626617-0.86152608 H 1.35340284 1.47626617 0.86152608 H 0.60178259-1.91021432-0.86152608 H 0.60178259-1.91021432 0.86152608 H -1.95518542 0.43394815-0.86152608 H -1.95518542 0.43394815 0.86152608 BHEt 3 B 0.00000000 0.00000000-0.16256530 C 1.57327143 0.00000000 0.36901716 C -0.78663572 1.36249303 0.36901716 C -0.78663572-1.36249303 0.36901716 C 2.49240748-1.05191527-0.28766400 C -0.33521839 2.68444583-0.28766400 C -2.15718909-1.63253056-0.28766400 H 3.52979726-1.03367055 0.08895235 H -0.86971367 3.57372937 0.08895235 S -11
H -2.66008359-2.54005882 0.08895235 H 2.10759648-2.06860647-0.13026204 H 0.73766751 2.85953532-0.13026204 H -2.84526399-0.79092885-0.13026204 H 2.53039473-0.89587832-1.37445651 H -0.48934398 2.63932527-1.37445651 H -2.04105075-1.74344696-1.37445651 H 1.59841508-0.15099970 1.46474950 H 2.03200384 0.99031645 0.20385323 H -0.66843796 1.45976792 1.46474950 H -1.87364113 1.26460872 0.20385323 H -0.92997712-1.30876822 1.46474950 H -0.15836271-2.25492517 0.20385323 H 0.00000000 0.00000000-1.41003983 BF 3 B 0.00000000 0.00000000 0.00000000 F 0.93818420 0.93818420 0.00000000 F 0.34339925-1.28158345 0.00000000 F -1.28158345 0.34339925 0.00000000 BHF 3 B 0.00000000 0.00000000-0.37832250 F 0.95203272 0.95203272 0.12942937 F 0.34846816-1.30050088 0.12942937 F -1.30050088 0.34846816 0.12942937 H 0.00000000 0.00000000-1.60298054 BH 2 SPh B -0.83069236-2.79961411 0.58081639 S 0.48275851-1.95634721-0.26395990 C 0.16189874-0.19106620-0.10130462 C -1.12202453 0.35738455-0.23659998 C -1.29935498 1.74218516-0.13527803 C -0.20182871 2.58448089 0.08636662 C 1.08031807 2.03406455 0.20478030 C 1.26560436 0.64942706 0.10851780 H -1.97502112-0.28675449-0.42240021 H -2.29569707 2.16284656-0.23848967 H -0.34422890 3.65858028 0.15987858 H 1.93755357 2.67937425 0.37456092 H 2.26024363 0.22454520 0.20619352 H -1.70123340-2.21086924 1.13400014 H -0.75996885-3.98695273 0.54664057 BH 3 SPh B 1.02250817 2.87774689 0.00000000 S -0.68361420 1.86668705 0.00000000 S -12
C -0.26128701 0.15741064 0.00000000 C 1.07537365-0.31056278 0.00000000 C 1.35651923-1.68162524 0.00000000 C 0.32749635-2.63645168 0.00000000 C -1.00343910-2.18384344 0.00000000 C -1.29264646-0.81720305 0.00000000 H 1.87811949 0.41866823 0.00000000 H 2.39524289-2.00905838 0.00000000 H 0.55335351-3.69992672 0.00000000 H -1.82117676-2.90318240 0.00000000 H -2.32727942-0.48198783 0.00000000 H 1.64799447 2.60864335 1.01220697 H 0.63893771 4.03612644 0.00000000 H 1.64799447 2.60864335-1.01220697 BH(SPh) 2 S 1.54290709-0.04758995 1.57736930 B 0.00000000 0.00000000 0.64374692 S -1.54290709 0.04758995 1.57736930 C 2.82172772 0.03665628 0.31293159 C -2.82172772-0.03665628 0.31293159 C 2.77493952 0.95760688-0.74486657 C 3.82434904 1.00752691-1.66989897 C 4.93037928 0.15798745-1.53615152 C 4.98148100-0.74738470-0.46900753 C 3.93111136-0.81092485 0.45482293 C -2.77493952-0.95760688-0.74486657 C -3.82434904-1.00752691-1.66989897 C -4.93037928-0.15798745-1.53615152 C -4.98148100 0.74738470-0.46900753 C -3.93111136 0.81092485 0.45482293 H 1.93198472 1.63344698-0.84433768 H 3.78128842 1.71988067-2.48906823 H 5.74540238 0.20531967-2.25228270 H 5.83659015-1.40750364-0.35417199 H 3.96883607-1.51988463 1.27625679 H -1.93198472-1.63344698-0.84433768 H -3.78128842-1.71988067-2.48906823 H -5.74540238-0.20531967-2.25228270 H -5.83659015 1.40750364-0.35417199 H -3.96883607 1.51988463 1.27625679 H 0.00000000 0.00000000-0.54130373 BH 2 (SPh) 2 S 1.53190452 0.00000000 1.36849748 B 0.00000000 0.00000000 0.14097686 S -1.53190452 0.00000000 1.36849748 C 2.94103241 0.00000000 0.30474169 S -13
C -2.94103241 0.00000000 0.30474169 C 2.86503298 0.00000000-1.10673253 C 4.02860258 0.00000000-1.88519145 C 5.29894212 0.00000000-1.29191948 C 5.38433336 0.00000000 0.11034141 C 4.22864806 0.00000000 0.89448871 C -2.86503298 0.00000000-1.10673253 C -4.02860258 0.00000000-1.88519145 C -5.29894212 0.00000000-1.29191948 C -5.38433336 0.00000000 0.11034141 C -4.22864806 0.00000000 0.89448871 H 1.89112583 0.00000000-1.58246555 H 3.93902723 0.00000000-2.96986298 H 6.19799751 0.00000000-1.90255279 H 6.35870614 0.00000000 0.59530234 H 4.30910682 0.00000000 1.97860090 H -1.89112583 0.00000000-1.58246555 H -3.93902723 0.00000000-2.96986298 H -6.19799751 0.00000000-1.90255279 H -6.35870614 0.00000000 0.59530234 H -4.30910682 0.00000000 1.97860090 H 0.00000000 1.01282712-0.52179366 H 0.00000000-1.01282712-0.52179366 B(SPh) 3 S 1.42383957 1.14051993-0.00041281 B -0.00041857 0.00059294 0.00003258 S -1.69991073 0.66379517 0.00001755 S 0.27480824-1.80284219-0.00005314 C 0.67212028 2.78226854-0.00087233 C -2.74510796-0.80864327 0.00066251 C 2.07245404-1.97293361 0.00015093 C 0.41835895 3.43536267-1.21600481 C -0.10077429 4.73557599-1.21301047 C -0.36078079 5.38889117-0.00164370 C -0.09835316 4.73725782 1.21010288 C 0.42075554 3.43703326 1.21385506 C 2.76629641-2.07242352 1.21515744 C 4.15178965-2.27329598 1.21185030 C 4.84622937-2.38257320 0.00036022 C 4.14933691-2.29133388-1.21119178 C 2.76384358-2.09028270-1.21463769 C -3.18606828-1.35416931-1.21400876 C -4.05144845-2.45470220-1.21016512 C -4.48390132-3.00825028 0.00160961 C -4.04858967-2.45590791 1.21291574 C -3.18321589-1.35537390 1.21582693 H 0.62250397 2.92900238-2.15388791 S -14
H -0.29991037 5.23686867-2.15595909 H -0.76241677 6.39799721-0.00194191 H -0.29560877 5.23985696 2.15275125 H 0.62671792 2.93194084 2.15202534 H 2.22679371-1.99022975 2.15317429 H 4.68650206-2.34578870 2.15467908 H 5.92091192-2.53959170 0.00044200 H 4.68212731-2.37784366-2.15392691 H 2.22241282-2.02174741-2.15264887 H -2.85199327-0.92302331-2.15220758 H -4.38767867-2.87719085-2.15280406 H -5.15608620-3.86134888 0.00197931 H -4.38262928-2.87931308 2.15592161 H -2.84701629-0.92511823 2.15367325 BH(SPh) 3 B 0.00000000 0.00000000 0.59628546 S 1.81325983 0.00000000 1.30328519 S -0.90662991-1.57032908 1.30328519 S -0.90662992 1.57032908 1.30328519 C -2.33784309-1.83762373 0.28104480 C -0.42250728 2.94344337 0.28104480 C 2.76035038-1.10581965 0.28104480 C -3.04611986-3.04774003 0.45765052 C -2.81065928-0.92575595-0.68544040 C -1.11636036 4.16188719 0.45765052 C 0.60360147 2.89698031-0.68544040 C 4.16248022-1.11414716 0.45765052 C 2.20705781-1.97122436-0.68544040 C -4.18129308-3.33697191-0.30463636 C -3.94563907-1.22508299-1.44877324 C -0.79925591 5.28959198-0.30463636 C 0.91186654 4.02956516-1.44877324 C 4.98054899-1.95262007-0.30463636 C 3.03377252-2.80448217-1.44877324 C -4.64209257-2.42798007-1.26973896 C 0.21835386 5.23416013-1.26973896 C 4.42373871-2.80618006-1.26973896 H -2.69323800-3.76235178 1.19674503 H -2.30120689 0.02045676-0.82339528 H -1.91167322 4.21358841 1.19674503 H 1.16831952 1.98267525-0.82339528 H 4.60491122-0.45123664 1.19674503 H 1.13288737-2.00313201-0.82339528 H -4.70572199-4.27722524-0.14755485 H -4.29089516-0.50406529-2.18656173 H -1.35132472 6.21388741-0.14755485 H 1.70891423 3.96805686-2.18656173 S -15
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