Sequential Hydrocarbon C—H Bond Activations by 16-Electron Organometallic Complexes of Molybdenum and Tungsten
2004; American Chemical Society; Linguagem: Inglês
10.1021/bk-2004-0885.ch011
ISSN1947-5918
Autores Tópico(s)Inorganic Chemistry and Materials
ResumoCp*M(NO)(hydrocarbyl)2 complexes (Cp* = η5-C5Me5) of molybdenum and tungsten exhibit hydrocarbyl-dependent thermal chemistry. Thus, gentle thermolysis of appropriate Cp*M(NO)(hydrocarbyl)2 precursors (M = Mo, W) results in the loss of hydrocarbon and the transient formation of 16-electron Cp*M(NO)-containing complexes such as Cp*M-(NO)(alkylidene), Cp*M(NO)(η2-benzyne), Cp*M(NO)(η2-acetylene), and Cp*M(NO)(η2-allene). These intermediates effect 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 Chapter summarizes the various types of C-H activations that have been effected with these organometallic nitrosyl complexes to date and presents some of the results of kinetic, mechanistic, and theoretical investigations of these processes.
Referência(s)