C(sp3)−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

doi:10.1002/chem.201703815

C(sp³)−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

Chemistry

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31 Scopus citations

Abstract

A detailed analysis of the C(sp³)−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 language	English (US)
Pages (from-to)	16097-16103
Number of pages	7
Journal	Chemistry - A European Journal
Volume	23
Issue number	63
DOIs	https://doi.org/10.1002/chem.201703815
State	Published - Nov 13 2017

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Organic Chemistry

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title = "C(sp3)−H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?",

abstract = "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.",

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AU - Nunes dos Santos Comprido, Laura

AU - Kästner, Johannes

AU - Hashmi, A. Stephen K.

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AB - 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.

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C(sp³)−H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?

Abstract

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