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• W2037157058 startingPage "1717" @default.
• W2037157058 abstract "A survey of carbon–carbon double bond lengths in transition metal vinyl complexes reveals a number of complexes with surprisingly short CC bonds. Accurate calculations with restricted Hartree–Fock (RHF) and density functional theory (DFT) methods on three examples with extremely short CC double bonds, Cp2ZrCl(–CHCHSiMe3), Cp*Ir(PMe3)(C2H3)(H) and Pt(PPh3)3(MeCCHMe)+, show that the short double bonds cannot be due to electronic or intramolecular steric effects. However, model calculations on Cp2ZrCl(–CHCHSiMe3) reveal that a disorder between two configurations of the CαCβ moiety could result in the apparent shortening of the CαCβ distance. The simulated structural parameters under this disorder model are completely consistent with the measured structure. A corresponding disorder model can be used to rationalize the shortening of the CC bond in Cp*Ir(PMe3)(C2H3)(H) and Pt(PPh3)3(MeCCHMe)+. Thus, these structures and perhaps other vinyl transition metal structures with short CC bonds could be subject to a similar disorder problem that results in an apparent shortening of the CC bonds." @default.
• W2037157058 created "2016-06-24" @default.
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• W2037157058 date "1999-04-01" @default.
• W2037157058 modified "2023-10-17" @default.
• W2037157058 title "On the origin of apparently short carbon–carbon double bonds in transition-metal vinyl complexes" @default.
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• W2037157058 doi "https://doi.org/10.1016/s0277-5387(99)00010-8" @default.
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