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Volumn 18, Issue 17, 1999, Pages 3414-3428

Hydrocarbon C-H Bond Activation by a Tungsten Acetylene Complex

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EID: 0000578113     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9904450     Document Type: Article
Times cited : (33)

References (65)
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    • This field has been extensively reviewed. See, for example: (a) Shilov, A. E.; Shul'pin, G. B Chem. Rev. 1997, 97, 2879. (b) Hill, C. L., Ed. Activation and Functionalization of Alkanes; Wiley-Interscience: New York; 1989. (c) Arndtsen, B. A.; Bergman, R. G.; Mobley, A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154.
    • (1997) Chem. Rev. , vol.97 , pp. 2879
    • Shilov, A.E.1    ShuL'pin, G.B.2
  • 2
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    • Wiley-Interscience: New York
    • This field has been extensively reviewed. See, for example: (a) Shilov, A. E.; Shul'pin, G. B Chem. Rev. 1997, 97, 2879. (b) Hill, C. L., Ed. Activation and Functionalization of Alkanes; Wiley-Interscience: New York; 1989. (c) Arndtsen, B. A.; Bergman, R. G.; Mobley, A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154.
    • (1989) Activation and Functionalization of Alkanes
    • Hill, C.L.1
  • 3
    • 0000820085 scopus 로고
    • This field has been extensively reviewed. See, for example: (a) Shilov, A. E.; Shul'pin, G. B Chem. Rev. 1997, 97, 2879. (b) Hill, C. L., Ed. Activation and Functionalization of Alkanes; Wiley-Interscience: New York; 1989. (c) Arndtsen, B. A.; Bergman, R. G.; Mobley, A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154.
    • (1995) Acc. Chem. Res. , vol.28 , pp. 154
    • Arndtsen, B.A.1    Bergman, R.G.2    Mobley, A.3    Peterson, T.H.4
  • 20
    • 85034138851 scopus 로고    scopus 로고
    • Unpublished results
    • In addition to the qualitative evidence described in ref 4c in support of a rate dependence on added silane, a quantitative study of the rate dependence on [silane] in the reaction depicted in eq 2 reveals a nonlinear dependence on [silane] (i.e., saturation kinetics) according to a mechanism involving reversible, rate-limiting dissociation of silane to form A, followed by a faster "trapping" step involving EtOAc. Legzdins, P.; Lumb, S. A. Unpublished results. Because the second step is the microscopic reverse of the first, it follows that the C-H activation step is also reversible.
    • Legzdins, P.1    Lumb, S.A.2
  • 31
    • 78649745802 scopus 로고    scopus 로고
    • Bergman and Mobley have recently described the interconversion of π-complexes prior to elimination of hydrocarbon. See: Mobley, T. A.; Bergman, R. G. J. Am. Chem. Soc. 1998, 120, 3253.
    • (1998) J. Am. Chem. Soc. , vol.120 , pp. 3253
    • Mobley, T.A.1    Bergman, R.G.2
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    • While Van't Hoff analyses yield more accurate free energy determinations, the thermal instability of the aryl vinyl complexes at elevated temperatures (>60°C) over the duration of the experiment obviates such an analysis
    • While Van't Hoff analyses yield more accurate free energy determinations, the thermal instability of the aryl vinyl complexes at elevated temperatures (>60°C) over the duration of the experiment obviates such an analysis.
  • 44
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    • Wiley: New York
    • Utilizing NMR spectroscopy, the rate of a chemical exchange process at the coalescence temperature of the exchanging magnetic environments is given by the equation k = πΔν/21/2, where Δν (Hz) is the frequency separation of the two signals at the low-temperature exchange limit. For more details, see: Günther, H. NMR Spectroscopy; Wiley: New York, 1980.
    • (1980) NMR Spectroscopy
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    • See, for example: (a) McDade, C.; Bercaw, J. E. J. Organomet. Chem. 1985, 279, 281. (b) Doherty, N. M.; McDade, C.; Bercaw, J. E. In Organometallic Compounds. Synthesis, Structure, and Reactivity, Vol. 1; Shapiro, B. L., Ed.; Texas A & M University Press: College Station, TX, 1983.
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  • 50
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    • 1-bonding interaction with the tungsten center to avoid an expansion of the valence shell to 20e
    • 1-bonding interaction with the tungsten center to avoid an expansion of the valence shell to 20e.
  • 58
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    • Hill, C. L., Ed.; John Wiley & Sons: New York, Chapter 1
    • (a) The hydromethylation of acetylene to propylene has been observed for complexes of iron, nickel, and platinum in the presence of methane, although the mechanism of this conversion is unknown and the homogeneity of these reactions is purported to be suspect. See: Shilov, A. E. In Activation and Functionalization of Alkanes; Hill, C. L., Ed.; John Wiley & Sons: New York, 1989; Chapter 1. (b) A zirconocene acetylene complex has been reported to activate the C-H bonds of the Cp ligand. See: Rosenthal, U.; Ohff, A.; Michalik, M.; Görls, H.; Burlakov, V. V.; Shur, V. B. Angew. Chem,. Int. Ed. Engl. 1993, 32, 1193. (c) A zirconocene benzyne complex has been reported to activate benzene C-H bonds. See: Erker, G. J. Organomet. Chem. 1977, 134, 189.
    • (1989) Activation and Functionalization of Alkanes
    • Shilov, A.E.1
  • 59
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    • (a) The hydromethylation of acetylene to propylene has been observed for complexes of iron, nickel, and platinum in the presence of methane, although the mechanism of this conversion is unknown and the homogeneity of these reactions is purported to be suspect. See: Shilov, A. E. In Activation and Functionalization of Alkanes; Hill, C. L., Ed.; John Wiley & Sons: New York, 1989; Chapter 1. (b) A zirconocene acetylene complex has been reported to activate the C-H bonds of the Cp ligand. See: Rosenthal, U.; Ohff, A.; Michalik, M.; Görls, H.; Burlakov, V. V.; Shur, V. B. Angew. Chem,. Int. Ed. Engl. 1993, 32, 1193. (c) A zirconocene benzyne complex has been reported to activate benzene C-H bonds. See: Erker, G. J. Organomet. Chem. 1977, 134, 189.
    • (1993) Angew. Chem,. Int. Ed. Engl. , vol.32 , pp. 1193
    • Rosenthal, U.1    Ohff, A.2    Michalik, M.3    Görls, H.4    Burlakov, V.V.5    Shur, V.B.6
  • 60
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    • (a) The hydromethylation of acetylene to propylene has been observed for complexes of iron, nickel, and platinum in the presence of methane, although the mechanism of this conversion is unknown and the homogeneity of these reactions is purported to be suspect. See: Shilov, A. E. In Activation and Functionalization of Alkanes; Hill, C. L., Ed.; John Wiley & Sons: New York, 1989; Chapter 1. (b) A zirconocene acetylene complex has been reported to activate the C-H bonds of the Cp ligand. See: Rosenthal, U.; Ohff, A.; Michalik, M.; Görls, H.; Burlakov, V. V.; Shur, V. B. Angew. Chem,. Int. Ed. Engl. 1993, 32, 1193. (c) A zirconocene benzyne complex has been reported to activate benzene C-H bonds. See: Erker, G. J. Organomet. Chem. 1977, 134, 189.
    • (1977) J. Organomet. Chem. , vol.134 , pp. 189
    • Erker, G.1
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    • Chemical Crystallography Laboratory, University of Oxford: Oxford, England
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    • (1995) CRYSTALS
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