A detailed analysis of the C(sp 3 )−H activation process by vinylidene Au I 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.
All Science Journal Classification (ASJC) codes
- Organic Chemistry