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Volumn 49, Issue 20, 2010, Pages 9162-9168

Calculation of dramatic differences in the activation energy of phenyl migratory insertion in the isomers of [Rh(PMe3)2Cl(CO)(Ph) H]: Important effects from both the ligand trans to Ph and the ligand trans to CO

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EID: 78549264514     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic100198u     Document Type: Article
Times cited : (8)

References (77)
  • 9
    • 78549263264 scopus 로고    scopus 로고
    • Dekker: New York
    • (d) Watson, D. J. Chemical Industries; Dekker: New York, 1998; Vol. 75, p 369.
    • (1998) Chemical Industries , vol.75 , pp. 369
    • Watson, D.J.1
  • 50
    • 0005609412 scopus 로고
    • For a discussion of the origin of distortion in this complex see ref 19 by Goldman and: a
    • For a discussion of the origin of distortion in this complex see ref 19 by Goldman and: (a) El-Idrissi, I.; Eisenstein, O.; Jean, Y. New J. Chem. 1990, 14, 671.
    • (1990) New J. Chem. , vol.14 , pp. 671
    • El-Idrissi, I.1    Eisenstein, O.2    Jean, Y.3
  • 52
    • 0001576239 scopus 로고    scopus 로고
    • For examplesin which reductive elimination in octahedral complexes is precededby geometry isomerizationsee: a
    • For examplesin which reductive elimination in octahedral complexes is precededby geometry isomerizationsee: (a) Rosini, G. P.; Wang, K.; Patel, B.; Goldman, A. S. Inorg. Chim. Acta 1998, 270, 537.
    • (1998) Inorg. Chim. Acta. , vol.270 , pp. 537
    • Rosini, G.P.1    Wang, K.2    Patel, B.3    Goldman, A.S.4
  • 54
    • 78549281986 scopus 로고    scopus 로고
    • - where the Ir-I bond trans to the methyl in the cis, fac isomer decreases from 2.93 to 2.75 å eq 4, and the Ir-CO bond trans to the methyl in the cis, mer isomer decreases from 1.98 to 1.86 å eq 5. Haynes argued that the contraction inthe Ir-CO bond enables CO to become a more effective π-acceptor in the TS, thus leadingto a smaller reaction barrier in the cis, mer isomer eq 5. The fact that the migrating phenyl and methyl groups are strong σ-donor ligands suggests that the systematic decrease in the Rh-H, Rh-Cl, Ir-I, and Ir-CO bonds in all of these TSs follows at least in part from creation of more favorable conditions for σ-interaction between each of these ligands and the metal as the migrating group is removed from the trans site in the TS
    • - where the Ir-I bond trans to the methyl in the cis, fac isomer decreases from 2.93 to 2.75 å (eq 4), and the Ir-CO bond trans to the methyl in the cis, mer isomer decreases from 1.98 to 1.86 å (eq 5). Haynes argued that the contraction inthe Ir-CO bond enables CO to become a more effective π-acceptor in the TS, thus leadingto a smaller reaction barrier in the cis, mer isomer (eq 5). The fact that the migrating phenyl and methyl groups are strong σ-donor ligands suggests that the systematic decrease in the Rh-H, Rh-Cl, Ir-I, and Ir-CO bonds in all of these TSs follows at least in part from creation of more favorable conditions for σ-interaction between each of these ligands and the metal as the migrating group is removed from the trans site in the TS.
  • 55
    • 0001739136 scopus 로고
    • For examples in which π-arguments were used to account for the reactivity of insertion in other octahedral complexes: a
    • For examples in which π-arguments were used to account for the reactivity of insertion in other octahedral complexes: (a) Kubota, M.; McClesky, T. M.; Hayashi, R. K.; Webb, C. G. J. Am. Chem. Soc. 1987, 109, 7569.
    • (1987) J. Am. Chem. Soc. , vol.109 , pp. 7569
    • Kubota, M.1    McClesky, T.M.2    Hayashi, R.K.3    Webb, C.G.4
  • 65
    • 0038626673 scopus 로고    scopus 로고
    • revision B.05; Gaussian, Inc.: Pittsburgh, PA
    • Gaussian 03, revision B.05; Gaussian, Inc.: Pittsburgh, PA, 2003.
    • (2003) Gaussian 03


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