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• W2053669777 endingPage "1506" @default.
• W2053669777 startingPage "1461" @default.
• W2053669777 abstract "The electronic and structural characteristics of the reaction interconverting a l-alkyne complex into a vinylidene via a 1,2 hydrogen shift are examined. In a mononuclear system, initial slippage of the alkyne to an η1 geometry is indicated. The subsequent step is shown to be analogous to the isomerization of a methylvinyl cation. We conclude that an alternative route involving a hydrido-acetylide species will be of much higher energy. A concerted shift in binuclear and trinuclear systems is ruled out, based on the loss of a strong bonding interaction between the alkyne and the metallic piece, in the transition state. In trinuclear systems, a mechanism for the isomerization is suggested involving prior oxidative addition of the CH bond across a metal-metal bond. The metallic piece in this case assists the transformation. The discussion is extended to other reactions featuring hydrogen shifts; these include the intramolecular formation of a binuclear vinylidene from a 1,2-hydrido-acetylide complex, the isomerization of a binuclear μ-alkylidyne into a μ-vinyl geometry and the transfer of a bridging hydrogen onto a capping hydrocarbon fragment in trinuclear cluster complexes." @default.
• W2053669777 created "2016-06-24" @default.
• W2053669777 creator A5001331359 @default.
• W2053669777 creator A5006026826 @default.
• W2053669777 date "1985-09-25" @default.
• W2053669777 modified "2023-10-18" @default.
• W2053669777 title "Hydrogen Migration in Transition Metal Alkyne and Related Complexes" @default.
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