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C(sp 3 )−H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?
Author(s) -
Klein Johannes E. M. N.,
Knizia Gerald,
Nunes dos Santos Comprido Laura,
Kästner Johannes,
Hashmi A. Stephen K.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703815
Subject(s) - lone pair , chemistry , hydride , triple bond , crystallography , stereochemistry , medicinal chemistry , double bond , polymer chemistry , molecule , organic chemistry , metal
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.