How electron flow controls the thermochemistry of the addition of olefins to nickel dithiolenes: predictions by density functional theory.

Abstract

The reaction of a nickel dithiolene complex (1) and ethylene is a two-step process, in which the trans-product (2) forms first in the direct addition of the olefin to 1, while the more thermodynamically stable cis-product (3) involves isomerization of 2. The introduction of electron-withdrawing groups (cyano or trifluoromethyl) not only significantly lowers the activation energy (TS1) for the formation of trans-product, but it also strongly stabilizes the products (2, 3) such that they are favored by the free energy. However, these substituents leave the barrier for the conformational transformation step (TS2) nearly unchanged. On reduction, the previously favored adduct is now strongly disfavored.

Cite this paper

@article{Fan2002HowEF, title={How electron flow controls the thermochemistry of the addition of olefins to nickel dithiolenes: predictions by density functional theory.}, author={Yubo Fan and Michael B. Hall}, journal={Journal of the American Chemical Society}, year={2002}, volume={124 41}, pages={12076-7} }