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Volumn 46, Issue 12, 2007, Pages 2104-2107

Dehydroiodination of iodo- and diiodomethane by a transient phosphinidene complex

Author keywords

Dehydroiodination; Elimination reactions; P ligands; Reaction mechanisms; Tungsten

Indexed keywords

CHEMICAL BONDS; CHEMICAL REACTIONS; COMPLEXATION; PHOSPHORUS COMPOUNDS;

EID: 34250865707     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200602617     Document Type: Article
Times cited : (13)

References (33)
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    • a) V. Plack, J. Goerlich, R. Schmutzler, Z. Anorg. Allg. Chem. 1998, 624, 1940-1942, and references therein;
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    • 5-Phosphinines: R. Streubel in Science of Synthesis, 15, Thieme, New York, 2005, pp. 1157-1179.
    • 5-Phosphinines": R. Streubel in Science of Synthesis, Vol. 15, Thieme, New York, 2005, pp. 1157-1179.
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    • 4th ed, Elsevier, Amsterdam
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    • Corbridge, D.E.C.1
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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.
    • 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.
  • 17
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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
    • 2J(P,H) = 12.7 Hz).
  • 18
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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
    • -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.
  • 22
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    • Gaussian03, RevB.02, 2003, Gaussian Inc. B3LYP: A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
    • Gaussian03, RevB.02, 2003, Gaussian Inc. B3LYP: A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
  • 23
    • 26844534384 scopus 로고    scopus 로고
    • 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;
    • 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;
  • 25
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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.
    • 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.
  • 26
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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;
    • 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;
  • 33
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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.
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.