Search

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. [ABSTRACT FROM AUTHOR]

A quantum chemical investigation of the Bu4N[Fe(CO)3(NO)]-catalyzed Cloke-Wilson rearrangement of vinyl cyclopropanes is reported. It was found that allylic CC bond activation can proceed through a SN2′ or SN2-type mechanism. The application of the recently reported intrinsic bond orbital (IBO) method for all structures indicated that one FeN π bond is directly involved. Further analysis showed that during the reaction oxidation occurs at the NO ligand exclusively. [ABSTRACT FROM AUTHOR]