Dioxygen insertion into the gold(i)-hydride bond: spin orbit coupling effects in the spotlight for oxidative addition.

ABSTRACT: O₂ insertion into a Au(i)-H bond occurs through an oxidative addition/recombination mechanism, showing peculiar differences with respect to Pd(ii)-H, for which O₂ insertion takes place through a hydrogen abstraction mechanism in the triplet potential energy surface with a pure spin transition state. We demonstrate that the spin-forbidden Au(i)-hydride O₂ insertion reaction can only be described accurately by inclusion of spin orbit coupling (SOC) effects. We further find that a new mechanism involving two O₂ molecules is also feasible, and this result, together with the unexpectedly high experimental entropic activation parameter, suggests the possibility that a third species could be involved in the rate determining step of the reaction. Finally

SUBMITTER: Gaggioli CA 

PROVIDER: S-EPMC6413884 | biostudies-literature | 2016 Dec

REPOSITORIES: biostudies-literature