Electronic Supplementary Material (ESI) for Chemical Communications This journal is The Royal Society of Chemistry 2013

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1 General. All manipulations were carried out under an inert atmosphere of dry nitrogen using standard Schlenk techniques or in an inert-atmosphere glove-box. Solvents were dried form the appropriate drying agent, distilled, degassed and stored over 4 Å molecular sieves. 1 H and 13 C NMR spectra were recorded on Varian 400 and 500 MHz spectrometers. The solution-phase 31 P and 77 Se spectra were recorded on a Varian 400 MHz spectrometer that was equipped with a X{ 1 H} broadband-observe probe. All spectra were recorded in C 6 D 6 at 300 K, unless stated otherwise. The 1 H and 13 C NMR chemical shifts are were measured relative to residual solvent peaks and reported relative to Me 4 Si; 31 P and 77 Se were externally referenced to H 3 PO 4 (aq) and Me 2 Se, respectively. The data for the X-ray structures were collected at 173 K on a Nonius Kappa CCD diffractometer [λ (Mo, Kα) Å] and refined using the SHELXL-97 software package. 1 [Ge(BDI)(PCy 2 )] (1) was made according to published procedures. 2 [CH{(CH 3 ) 2 CN-2,6-iPr 2 C 6 H 3 } 2 GeSeP(C 6 H 11 ) 2 ], (2). Selenium (0.02 g, mmol), finely suspended in toluene, was added dropwise to a solution of β- diketiminate germanium dicyclohexylphosphide (0.20 g, mmol) in toluene (5 ml), and the mixture was stirred for 24 hrs at room temperature resulting in the colour changing from purple to orange. The solvent was filtered, concentrated in vacuo and stored at -27 C for 24 hrs yielding [Ge(L)SeP(C 6 H 10 ) 2 ], (0.05 g, 21%, first crop) as orange crystals. 1 H NMR (C 6 D 6, 293 K): δ 7.13 (dd, J = 7.6 Hz, 2H, m-h), 7.08 (t, J = 7.6 Hz, 2H, p-h), 7.00 (dd, J = 7.6 Hz, 2H, m-h), 4.65 (s, 1H, γ-ch), 3.64 (septet, J = 6.8 Hz, 2H, CHMe 2 ), 3.28 (septet, J = 6.8 Hz, 2H, CHMe 2 ), 1.61 (d, J = 6.8 Hz, 6H, CHMe 2 ), (br, 4H, Cy-CH 2 ), 1.50 (s, 6H, NCMe), (br, 6H, Cy-CH 2 ), 1.37 (d, J = 6.8 Hz, 6H, CHMe 2 ), 1.15 (d, J = 6.8 Hz, 6H, CHMe 2 ), 1.10 (d, J = 6.8 Hz, 6H, CHMe 2 ), (br, 10H, Cy-CH 2 ), 0.67 (br, 2H, Cy- CH 2 ). 13 C{ 1 H} NMR ( MHz, C 6 D 6, 293 K): δ (NCMe), (ipso-c), (o-c), (o-c), (p-c), (m-c), (m-c), 95.8 (γ-ch), 34.9 (Cy-CH2), 34.6 (Cy-CH2), 29.8 (d, JCP = 18.1 Hz, Cy-CH), 29.2 (d, JCP = 7.0 Hz, CHMe 2 ), 29.1 (Cy-CH2), 28.5 (CHMe 2 ), 27.3 (CHMe 2 ), 27.2 (PCy), 27.2 (PCy), 27.1 (CHMe 2 ), 26.7 (PCy), 26.6 (PCy), 26.5 (PCy), 24.9 (PCy), 24.4 (CHMe 2 ), 24.2 (CHMe 2 ), 22.7 (NCMe). 31 P{ 1 H} NMR ( MHz, C 6 D 6, 293 K): δ 42 (J PSe = 198 Hz). 77 Se { 1 H} NMR (76.19 MHz, C 6 D 6, 293 K): (J SeP = 198 Hz). IR (Nujol,

2 cm -1 ) 1556 (s), 1317 (s), 1172 (s), 1099 (s), 1016 (s), 848 (s), 798 (s), 722 (s), 518 (s). Anal. calc. for C41H63N2PSeGe: C, 64.24; H, 8.28; N, Found: C, 65.46; H, 8.00; N, 3.18%. [CH{(CH3)CN-2,6-iPr2C6H3}2GeSeP(=Se)(C6H11)2], (3). [(BDI)GePCy2] (1) (0.19 g, 0.27 mmol) in toluene (10 ml) was added to an excess of elemental selenium (0.09 g, 1.10 mmol) suspended in toluene (5mL). The mixture was stirred rapidly at room temperature for 20 h, then filtered through a pad of Celite. Volatiles were removed from filtrate under vacuum. The yellow solid residue was washed with cold pentane (3 x ~ 3 ml). Single crystals of [(BDIDIPP)GeSeP(Se)Cy2] (4) were found along with crystals of [(BDIDIPP)Ge(Se)PCy2] (3) and separated from a concentrated toluene solution at 30 C. Yield: 0.15 g, 64% (combined yield with 4). 1 H NMR ( MHz, C6D6, 303K): δ 7.12 (br, 6H, Ar-H), 4.68 (s, 1H, γ-ch), 3.50 (septet, J = 6.8 Hz, 2H, CHMe2), 3.31 (septet, J = 6.8, 2H, CHMe2), 1.74 (br, 2H, Cy-CH2), 1.67 (d, J = 6.4 Hz, 8H, CHMe2 and Cy-CH2), 1.59 (d, J = 6.4 Hz, 8H, CHMe2 and Cy-CH2), 1.53 (s, 12H, 287 NCMe, Cy-CH2), 1.16 (d, J = 6.4 Hz, 6H, CHMe2), 1.13 (d, J = 6.8 Hz, 6H, CHMe2), 1.03 (br, 6H, Cy-CH2, Cy-CH). 13 C{ 1 H} NMR ( MHz, C6D6, 303K): δ (NCMe), (ipso-c), (o-c), (o-c), (p-c), (m-c), (m- C), 96.5 (γ-ch), 43.1 (d, JCP = 38 Hz, Cy-CH), 29.8, 27.1 (CHMe2), 26.9, 26.7 (Cy-CH2), 26.6, 25.7, 24.9, 23.6 (CHMe2), 21.8 (NCMe). 31 P{ 1 H} NMR ( MHz, C6D6, 303K): δ 63.7 (JPSe = 551 Hz). 77 Se NMR (76.19 MHz, C6D6, 303K): δ 18 (d, JSeP = 198 Hz). [CH{(CH3)CN-2,6-iPr2C6H3}2Ge(Se)P(C6H11)2], (4). Compound 4 was co-crystallised from the synthesis of [(BDIDIPP)GeSeP(Se)Cy2] (2). 1 H NMR ( MHz, CDCl3, 303K): δ 7.32 (d, J = 4.8 Hz, 3H, Ar-H), 7.19 (br, 3H, Ar-H), 5.45 (s, 1H, γ-ch), 4.01 (septet, J = 6.4 Hz, 2H, CHMe2), 3.53 (septet, J = 6.8 Hz, 2H, CHMe2), 2.24 (br, 3H, Cy-CH2), 1.91 (s, 6H, NCMe), 1.45 (d, J 289 = 7.2 Hz, 6H, CHMe2), 1.43 (d, J = 6.8 Hz, 6H, CHMe2), (br, 6H, Cy-CH2), 1.21 (d, J = 6.8 Hz, 6H, CHMe2), (br, 3H, Cy-CH2), 1.06 (d, J = 6.8 Hz, 6H, CHMe2), (br, 14H, Cy-CH2). 13 C{ 1 H} NMR ( MHz, CDCl3, 303K): δ (NCMe), (ipso-c), (o-c), (o-c), (p-c), (m-c), (m-c), 98.9 (γ-ch), 34.5 (d, JCP = 16 Hz, Cy-CH), 34.3 (CHMe2), 32.0 (CHMe2), 29.7 (CHMe2), 29.1, 27.9, 27.7, 27.4, 26.5 (Cy-CH2), 25.5, 25.2, 24.4

3 (CHMe2), 21.7 (NCMe). 31 P{ 1 H} NMR ( MHz, CDCl3, 303K): δ Se NMR (76.19 MHz, CDCl3, 303K): δ 91 (d, JSeP = 12 Hz). 1. G. M. Sheldrick, SHELXL-97, Program for the Refinement of Crystal Structures, Göttingen, E. C. Y. Tam, N. A. Maynard, D. C. Apperley, J. D. Smith, M. P. Coles and J. R. Fulton, Inorg Chem, 2012, 51, Computational. All calculations were carried out using the B3LYP 3-6 density functional and the TZVP basis set 7 with the Gaussian 09 suite of programs 8. All stationary points were confirmed to be minima through the calculation of the forceconstants. Energies reported are pure electronic energies (without ZPVE correction) and thermodynamic free energies (ΔG). All energy values are reported in kj/mol. The Natural Bonding Orbital (NBO) analysis 9,10 carried out is based on the NBO 3.1 implementation included in Gaussian09. The Wiberg bond indices 11 discussed in the manuscript were calculated with the same program. 3. A.D. Becke, J.Chem.Phys. 1993, C. Lee, W. Yang, R.G. Parr, Phys. Rev. B, 1988, 37, S.H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, J.Phys.Chem., 1994, 98, A. Schaefer, C. Huber, and R. Ahlrichs, J. Chem. Phys., 1994, 100, Gaussian 09, Revision B.1, 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, Jr., 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, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, A. E. Reed, R. B. Weinstock, and F. Weinhold, J. Chem. Phys., 1985, 83, A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev., 1988, 88, K. B. Wiberg, Tetrahedron, 1968, 24, 1083 Compound 1 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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6 Compound 2 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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9 Compound 3 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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11 Compound 4 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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14 Compound A Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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16 Compound B Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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19 Cy 2 PHSe Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

20 Cy 2 PSeH Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

21 [Cy 2 PSe] Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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