Carbon-hydrogen bond activation in cyclopentadienyl dimethyl tungsten nitrosyl and carbonyl Academic Article

abstract

• Mechanisms for generating tungsten carbene complexes from CpW(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.

authors

• Hall, Michael

published proceedings

• Journal of the Chemical Society, Dalton Transactions

author list (cited authors)

• Fan, Y., & Hall, M. B.

complete list of authors

• Fan, Y||Hall, MB

publication date

• November 2002

published in

• Journal of the Chemical Society, Dalton Transactions  Journal

start page

• 713

end page

• 718

issue

• 5