Supporting Information for: Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX 3 Compounds

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1 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 Department of Chemistry, Villanova University, Villanova, Pennsylvania 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

2 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 = V (Co II/I ). S -2

3 Figure S2. Cyclic voltammogram of [Co(dedpe) 2 (CH 3 CN)] 2+ in acetonitrile. E 1/2 = V (Co II/I ); V (Co I/0 ); 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

4 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 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 = (3) Å, b = (3) Å, c = (1) Å, β = (1), V = (2) Å reflections (R int = ) were collected (15442 unique) over θ = 2.12 to 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 = 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 with R1(wR2) (0.1274) for [Iθ>2(I)] and with largest difference peak and hole of and 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 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 = (1), c = (1) Å, β = (1), V = S -4

5 2813.8(1) Å reflections (R int = ) were collected (5076 unique) over θ = 3.65 to 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 = 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 with R1(wR2) (0.0923) for [Iθ>2(I)] and with largest difference peak and hole of and 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 color, habit red, blocks orange, blocks crystal system monoclinic monoclinic space group P2(1)/c P2(1)/n a, Å (3) (2) b, Å (3) (2) c, Å (9) (5) α, deg β, deg (10) (10) γ, deg V(Å 3 ) (19) (9) λ, Å (Cu (Mo), Kα) ( ) Z 4 4 density (g/cm 3 ) temperature (K) 100(2) 100(2) 2θ range, deg µ(cu (Mo), Kα), mm -1 (0.715) R(F), Rw(F) , , 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

6 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 , 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

7 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

8 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 BH BEt BHEt BF BHF BH 2 SPh BH 3 SPh B(OPh) BH(OPh) BH(SPh) BH 2 (SPh) B(SPh) BH(SPh) B(OC 6 F 5 ) BH(OC 6 F 5 ) S -8

9 Table 2S. Energies (a.u.) calculated at B3LYP/aug-cc-pVTZ//B3LYP/DZVP2 level of theory. Species Electronic E BH BH BEt BHEt BF BHF BH 2 SPh BH 3 SPh B(OPh) BH(OPh) BH(SPh) BH 2 (SPh) B(SPh) BH(SPh) B(OC 6 F 5 ) BH(OC 6 F 5 ) S -9

10 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 BF B(OPh) BH 2 SPh BH(SPh) B(SPh) B(OC 6 F 5 ) 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 BF B(OPh) BH 2 SPh BH(SPh) B(SPh) B(OC 6 F 5 ) Grant, D. J.; Dixon, D. A.; Camaioni, D.; Potter, R. G.; Christe, K. O. Inorg. Chem. 2009, 48, S -10

11 Cartesian coordinates of structures optimized at B3LYP/DZVP2 level of theory BH 3 B H H H BH 4 B H H H H BEt 3 B C C C C C C H H H H H H H H H H H H H H H BHEt 3 B C C C C C C H H S -11

12 H H H H H H H H H H H H H H BF 3 B F F F BHF 3 B F F F H BH 2 SPh B S C C C C C C H H H H H H H BH 3 SPh B S S -12

13 C C C C C C H H H H H H H H BH(SPh) 2 S B S C C C C C C C C C C C C H H H H H H H H H H H BH 2 (SPh) 2 S B S C S -13

14 C C C C C C C C C C C H H H H H H H H H H H H B(SPh) 3 S B S S C C C C C C C C C C C C C C C C C C H S -14

15 H H H H H H H H H H H H H H BH(SPh) 3 B S S S C C C C C C C C C C C C C C C C C C H H H H H H H H H H S -15

16 H H H H H H B(OPh) 3 B C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H O O O BH(OPh) 3 B S -16

17 C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H O O O H B(OC 6 F 5 ) 3 B C C C C C C C C S -17

18 C C C C C C C C C C F F F F F F F F F F F F F F F O O O BH(OC 6 F 5 ) 3 B C C C C C C C C C C C C C C C C C S -18

19 C F F F F F F F F F F F F F F F O O O H S -19