Computational evidence that the inverse kinetic isotope effect for reductive elimination of methane from a tungstenocene methyl–hydride complex is associated with the inverse equilibrium isotope effect for formation of a σ-complex intermediate†
Kevin E. Janak,David G. Churchill,Gerard Parkin
Chemical Communications Pub Date : 11/28/2002 00:00:00 , DOI:10.1039/B209684F
Abstract
Calculations on [H2Si(C5H4)2]W(Me)H demonstrate that the interconversion between [H2Si(C5H4)2]W(Me)H and the σ-complex [H2Si(C5H4)2]W(σ-HMe) is characterized by normal kinetic isotope effects for both reductive coupling and oxidative cleavage; the equilibrium isotope effect, however, is inverse and is the origin of the inverse kinetic isotope effect for the overall reductive elimination of methane.
