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Thermal activation of hydrocarbon C-H bonds by Cp*M(NO) complexes of molybdenum and tungsten

TitleThermal activation of hydrocarbon C-H bonds by Cp*M(NO) complexes of molybdenum and tungsten
Publication TypeJournal Article
Year of Publication2003
AuthorsPamplin, CB, Legzdins, P
JournalAccounts of Chemical Research
Volume36
Pagination223-233
Date PublishedApr
Type of ArticleReview
ISBN Number0001-4842
KeywordsALKANES, ALKYLIDENE COMPLEXES, ARENES, CHEMISTRY, INTERMEDIATE, NITROSYL, REACTIVITY, REDUCTIVE ELIMINATION, THERMOLYSIS, TRANSITION-METAL BONDS
Abstract

Gentle thermolysis of appropriate Cp*M(NO)(hydrocarbyl)(2) complexes (Cp* = eta(5)-C5Me5) of molybdenum and tungsten results in loss of hydrocarbon and the transient formation of 16-electron Cp*M(NO)-containing complexes such as Cp*M(NO)(alkylidene), Cp*M(NO)(eta(2)-benzyne), Cp*M(NO)(eta(2)-acetylene), and Cp*M(NO)(eta(2)-allene) (M = Mo, W). These intermediates effect the single, double, or triple activation of hydrocarbon C-H bonds intermolecularly, the first step of these activations being the reverse of the transformations by which they were generated. This Account summarizes the various types of C-H activations that have been effected with these nitrosyl complexes and also describes the results of kinetic, mechanistic, and theoretical investigations of these processes.

URL<Go to ISI>://000182343300001