Carbon–hydrogen bond activation in cyclopentadienyl dimethyl tungsten nitrosyl and carbonyl

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 (σ-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 Å longer than the W-H single bond in the oxidative addition intermediate. Stronger π backbonding of the NO ligand is responsible for the difference. © The Royal Society of Chemistry 2002.

Carbon–hydrogen bond activation in cyclopentadienyl dimethyl tungsten nitrosyl and carbonyl Conference Paper