C(sp 3 )-H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?

Authors :: Klein JEMN
Knizia G
Nunes Dos Santos Comprido L
Kästner J
Hashmi ASK
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2017 Nov 13; Vol. 23 (63), pp. 16097-16103. Date of Electronic Publication: 2017 Oct 19.
Publication Year :: 2017
Abstract: A detailed analysis of the C(sp <superscript>3</superscript> )-H activation process by vinylidene Au <superscript>I</superscript> 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.<br /> (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Full Text Access

Tools