C(sp3 )-H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?
Johannes E M N KleinGerald KniziaLaura Nunes Dos Santos CompridoJohannes KarwounopoulosA Stephen K HashmiPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2017)
A detailed analysis of the C(sp3 )-H activation process by vinylidene AuI complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C-C bond formation, and (iii) σ to π rearrangement of the lone pair coordinated to Au. Small perturbations of the system lead to either a concerted asynchronous reaction, or a stepwise reaction featuring an intermediate with a C-H-C three-centre two-electron (3c-2e) bond. The role of π-donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies.