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Recent Mechanistic and Synthetic Developments in the Chemistry of Transition-Metal Vinylidene Complexes

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JournalChemistry - A European Journal
DatePublished - 26 Jul 2010
Issue number28
Volume16
Number of pages10
Pages (from-to)8238-8247
Original languageEnglish

Abstract

Transition-metal vinylidene complexes are intermediates in a number of synthetically important transformations of alkynes. Underpinning these applications is the ability of various electron-rich transition-metal complexes to effectively facilitate the conversion of alkynes into their vinylidene tautomers. Recent experimental and theoretical studies have provided considerable insight into the mechanisms by which this process occurs and they are detailed herein. In particular, it has been demonstrated that different substituents on both the metal and the alkyne may have profound effects on both the kinetic and thermodynamic profiles of the alkyne/vinylidene tautomerisation. An important finding is that internal alkynes may be employed to prepare disubstituted vinylidene complexes under easily accessible conditions. This discovery brings to light a new facet of the potential synthetic applications of transition metal vinylidene complexes.

    Research areas

  • alkynes, half-sandwich complexes, rhodium, ruthenium, vinylidenes, HALF-SANDWICH COMPLEXES, CARBON-CARBON BONDS, TERMINAL ALKYNES, SOLID-STATE, INTERNAL ALKYNONES, RHODIUM COMPLEXES, RUTHENIUM, ISOMERIZATION, LIGANDS, TRANSFORMATION

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