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

doi:10.1002/chem.201703815

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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

29 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 language	English
Pages (from-to)	16097-16103
Number of pages	7
Journal	Chemistry
Volume	23
Issue number	63
DOIs	https://doi.org/10.1002/chem.201703815
Publication status	Published - 13-Nov-2017
Externally published	Yes

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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@article{7b865b0a32c64d6c8eb0d9d743d89ed4,

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

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.",

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",

author = "Klein, {Johannes E. M. N.} and Gerald Knizia and {Nunes dos Santos Comprido}, Laura and Johannes K{\"a}stner and Hashmi, {A. Stephen K.}",

year = "2017",

month = nov,

day = "13",

doi = "10.1002/chem.201703815",

language = "English",

volume = "23",

pages = "16097--16103",

journal = "Chemistry",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",

number = "63",

}

TY - JOUR

T1 - C(sp(3))-H Bond Activation by Vinylidene Gold(I) Complexes

T2 - A Concerted Asynchronous or Stepwise Process?

AU - Klein, Johannes E. M. N.

AU - Knizia, Gerald

AU - Nunes dos Santos Comprido, Laura

AU - Kästner, Johannes

AU - Hashmi, A. Stephen K.

PY - 2017/11/13

Y1 - 2017/11/13

N2 - 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.

AB - 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.

KW - bond orbital analysis

KW - C-H activation

KW - computational chemistry

KW - gold(I)

KW - reaction mechanisms

KW - C-H BOND

KW - CONSISTENT BASIS-SETS

KW - CONVERGENT BASIS-SETS

KW - CATALYZED CYCLOISOMERIZATION

KW - ORGANIC-CHEMISTRY

KW - HYDRIDE TRANSFER

KW - EXACT EXCHANGE

KW - HYDROGEN-BOND

KW - FUNCTIONALIZATION

KW - DENSITY

U2 - 10.1002/chem.201703815

DO - 10.1002/chem.201703815

M3 - Article

SN - 0947-6539

VL - 23

SP - 16097

EP - 16103

JO - Chemistry

JF - Chemistry

IS - 63

ER -

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

Abstract

Keywords

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