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2 from a P ligand upon coordination to a tungsten center, see: E. Bannwart, H. Jacobsen, R. Hübener, H. W. Schmalle, H. Berke, J. Organomet. Chem. 2001, 622, 97-111.
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2 from a P ligand upon coordination to a tungsten center, see: E. Bannwart, H. Jacobsen, R. Hübener, H. W. Schmalle, H. Berke, J. Organomet. Chem. 2001, 622, 97-111.
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17
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34250892180
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Selected NMR (CDC13, 25°C; ext. TMS (1H, 13C) or ext. 85% H3PO4 (31P, and MS data of complexes 3-5: 3: 1H NMR (200.0 MHz, δ, 0.31 (s, 9H, SiCH3, 0.34 (s, 9H, SiMe3, 1.85 (d, 2J(P,H, 3.6Hz, 1H, CHSiMe3, 3.02 ppm (d, 2J(P,H, 3.5 Hz, 3H, PCH3, 13C{ 1H} NMR (50.3 MHz, δ, 3.1 (d, 3J-(P,C, 3.7 Hz, SiCH3, 3.6 (d, 3J(P,C, 3.0 Hz, SiCH 3, 29.2 (d, 1J(P,C, 20.2 Hz, PCH3, 36.1 (d, 1J(P,C, 14.5 Hz, PCH, 198.6 (d, 1J(P,C, 7.8 Hz, cis-CO, 199.7 ppm (d, 12J(P,C, 22.9 Hz, trans-CO, 31P{ 1H} NMR (81.0 MHz, δ, 29.7 ppm (s, 1J(W,P, 263.1 Hz, MS 70 cV, EI, 184
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2J(P,H) = 12.7 Hz).
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18
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34250903826
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Crystal structure data for complex 5 (C14H 28I3O4PSi2W, orthorhombic, space group Pbca (no. 61, a, 17.5907(2, b, 17.4856(2, c, 34.6938(4) Å, V, 10671.3(2) Å3, Z, 16, ρ, 2.271 Mgm-3, μ(MoKα, 7.966 mm-1. A total of 47812 reflections were measured on a Nonius KappaCCD diffractometer using MoKα radiation (λ, 0.71073 Å) at a temperature of 123(2) K, 9412 reflections were unique (Rint, 0.0697, A semi-empirical absorption correction from equivalents was applied min./max. transmission, 0.21995/0.41737, The structure was solved with Patterson methods and refined with full-matrix least squares against F2 of all reflections. Non-hydrogen atoms were refined anisotropically, hydrogen atoms were refined as rigid groups. R values [I
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-3. CCDC-606431 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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19
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Gaussian03, RevB.02, 2003, Gaussian Inc. B3LYP: A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
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Gaussian03, RevB.02, 2003, Gaussian Inc. B3LYP: A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
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23
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Valence triple zeta + polarization basis 6-311g(d,p): R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650;
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Valence triple zeta + polarization basis 6-311g(d,p): R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650;
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25
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33745770836
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For iodine the 6-311g(d,p) basis set from the EMSL Gaussian basis set order form (www.emsl.pnl.gov/forms/basisform.html) was used. ECP LanL2DZ at W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270.
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For iodine the 6-311g(d,p) basis set from the EMSL Gaussian basis set order form (www.emsl.pnl.gov/forms/basisform.html) was used. ECP LanL2DZ at W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270.
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26
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36849122016
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Compliance constants (diagonal elements of the inverse of the matrix of force constants) are inversely proportional to the strength of a bond; the smaller the numerical value the less compliant it is. J. C. Decius, J. Chem. Phys. 1963, 38, 241;
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Compliance constants (diagonal elements of the inverse of the matrix of force constants) are inversely proportional to the strength of a bond; the smaller the numerical value the less compliant it is. J. C. Decius, J. Chem. Phys. 1963, 38, 241;
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33
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29044441359
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Recently, the synthesis of alkylidine (from alkylidene) complexes was achieved by dehydrohalogenation by a germylene derivative: S. R. Caskey, M. H. Stewart, Y.J. Ahn, M. J. A. Johnson, J. W. Kampf, Organometallics 2005, 24, 6074-6076.
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Recently, the synthesis of alkylidine (from alkylidene) complexes was achieved by dehydrohalogenation by a germylene derivative: S. R. Caskey, M. H. Stewart, Y.J. Ahn, M. J. A. Johnson, J. W. Kampf, Organometallics 2005, 24, 6074-6076.
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