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

Johannes E.M.N. Klein, Gerald Knizia, Laura Nunes dos Santos Comprido, Johannes Kästner, A. Stephen K. Hashmi

Research output: Contribution to journalArticle

21 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)16097-16103
Number of pages7
JournalChemistry - A European Journal
Volume23
Issue number63
DOIs
StatePublished - Nov 13 2017

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Fingerprint Dive into the research topics of 'C(sp <sup>3</sup> )−H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?'. Together they form a unique fingerprint.

  • Cite this