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Volumn 125, Issue 33, 2003, Pages 10093-10102

Kinetics and thermodynamics of H• transfer from (η 5-C5R5)Cr(CO)3H (R = Ph, Me, H) to methyl methacrylate and styrene

Author keywords

[No Author keywords available]

Indexed keywords

HYDRIDES; HYDROGENATION; OLEFINS; POLYMERIZATION; RATE CONSTANTS; STYRENE;

EID: 0043011088     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034927l     Document Type: Article
Times cited : (62)

References (78)
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    • term begins to consume 3; as we would expect, no such initial rise in [1a] is seen in the subsequent experiments at lower [MMA] in toluene.
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    • as modified by (b) Tilset, M.; Parker, V. D. J. Am. Chem. Soc. 1990, 112, 2843. Potential sources of error in the determination of M-H bond strengths by this method have been reviewed in ref 8 above.
    • (1990) J. Am. Chem. Soc. , vol.112 , pp. 2843
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    • Acidity of hydrido transition metal complexes in solution
    • Dedieu, A., Ed.; VCH: New York, Chapter 9
    • The work has been summarized in a review: Kristjánsdóttir, S. S.; Norton, J. R. "Acidity of Hydrido Transition Metal Complexes in Solution". In Transition Metal Hydrides; Dedieu, A., Ed.; VCH: New York, 1991, Chapter 9.
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    • Group addition thermochemical calculation using data from and methods of Pedley, J. B.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds; Chapman and Hall: London, 1986. This type of estimate should approximate the gas-phase enthalpy of formation.
    • (1986) Thermochemical Data of Organic Compounds
    • Pedley, J.B.1    Naylor, R.D.2    Kirby, S.P.3
  • 44
    • 0042523460 scopus 로고    scopus 로고
    • note
    • The C-H BDEs were estimated using three different approaches: thermolysis of azoalkanes, thermolysis of dimethyl tetramethylsuccinate, and ESR determination of carboalkoxyalkyl radical rotational barriers.
  • 45
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    • Kharasch, M. S. J. Res. Natl. Bur. Stand. 1929, 2, 359-430. It is unclear from the tables of thermodynamic data if the Kharasch measurement is a gas-phase enthalpy. If it is a condensed-phase measurement, then the heat of vaporization of methyl isobutyrate must be added to the measured value of - 117.3 kcal/mol, which would essentially make the Engel and Kharasch numbers equal.
    • (1929) J. Res. Natl. Bur. Stand. , vol.2 , pp. 359-430
    • Kharasch, M.S.1
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    • A similar "negative activation energy" has been seen, and a similar explanation (reversible formation of a dissociable intermediate) offered, for a carbene/alkene cycloaddition in Turro, N. J.; Lehr, G. F.; Butcher, J. A., Jr.; Moss, R. A.; Guo, W. J. Am. Chem. Soc. 1982, 104, 1754-1756.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 1754-1756
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  • 57
    • 0042523459 scopus 로고    scopus 로고
    • note
    • 3• (1a) and the tertiary radical 3-P will be weak. Formation of such a bond would reduce the efficiency of 1a as a chain transfer catalyst, as the resulting alkyl complex 5 cannot be an intermediate in formation of the hydride 2a (5 would have no vacant coordination site and thus be unable to undergo β-hydrogen elimination). Weak interaction between the metalloradical 1a and the carbon-centered radical 3-P can. however, contribute to the formation of the cage in Scheme 6.
  • 58
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    • Reversible formation of a Co-C bond has been observed with Co(II) chain transfer catalysts and the α-methylbenzyl radical 4 in styrene polymerization, but it is insignificant with the isobutyryl radical 3 in MMA polymerization. Heuts, J. P. A.: Forster, D. J.; Davis, T. P. Macromolecules 1999, 32, 2511-2519.
    • (1999) Macromolecules , vol.32 , pp. 2511-2519
    • Heuts, J.P.A.1    Forster, D.J.2    Davis, T.P.3
  • 59
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    • Similarly, the release of alkenes from alkyl cobalamins occurs not by β-hydrogen elimination but by C - Co H• transfer after homolysis of the Co-C bond. See Halpern, J. Pure Appl. Chem. 1979, 51, 2171, and Bonhôte, P.; Scheffold, R. Helv. Chim. Acta 1991, 74, 1425-1444.
    • (1979) Pure Appl. Chem. , vol.51 , pp. 2171
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    • Similarly, the release of alkenes from alkyl cobalamins occurs not by β-hydrogen elimination but by C - Co H• transfer after homolysis of the Co-C bond. See Halpern, J. Pure Appl. Chem. 1979, 51, 2171, and Bonhôte, P.; Scheffold, R. Helv. Chim. Acta 1991, 74, 1425-1444.
    • (1991) Helv. Chim. Acta , vol.74 , pp. 1425-1444
    • Bonhôte, P.1    Scheffold, R.2
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    • note
    • 2D exchange.)
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.