Theoretical studies of inorganic and organometallic reaction mechanisms. Part 21. Carbon-hydrogen bond activation in cyclopentadienyl dimethyl tungsten nitrosyl and carbonyl
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Mechanisms for generating tungsten carbene complexes from CpW(NO)(CH 3)2, Cp*W(NO)(CH3)2 CP*W(NO)(CH3)2 and [CpW(CO)(CH3) 2]- by methane elimination were studied by density functional (B3LYP) computations. Based on the calculations, a one-step (-bond metathesis like) mechanism is preferred in nitrosyl complexes, while a two-step (oxidative addition then reductive elimination) mechanism is preferred in the carbonyl complex. The one-step mechanism is strongly assisted by the metal as the transition state for this mechanism has a W-H distance that is only 0.1 longer than the W-H single bond in the oxidative addition intermediate. Stronger backbonding of the NO ligand is responsible for the difference. The Royal Society of Chemistry 2002.
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