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 Kaestner, A. Stephen K. Hashmi

Research output: Contribution to journalArticleAcademicpeer-review

25 Citations (Scopus)

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) sigma to pi 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 pi-donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies.

Original languageEnglish
Pages (from-to)16097-16103
Number of pages7
JournalChemistry
Volume23
Issue number63
DOIs
Publication statusPublished - 13-Nov-2017
Externally publishedYes

Keywords

  • bond orbital analysis
  • C-H activation
  • computational chemistry
  • gold(I)
  • reaction mechanisms
  • C-H BOND
  • CONSISTENT BASIS-SETS
  • CONVERGENT BASIS-SETS
  • CATALYZED CYCLOISOMERIZATION
  • ORGANIC-CHEMISTRY
  • HYDRIDE TRANSFER
  • EXACT EXCHANGE
  • HYDROGEN-BOND
  • FUNCTIONALIZATION
  • DENSITY

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