Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules

Wen Ching Chen; Wei Chih Shih; Titel Jurca; Lili Zhao; Diego M. Andrada; Chun Jung Peng; Chun Chi Chang; Shu Kai Liu; Yi Ping Wang; Yuh Sheng Wen; Glenn P.A. Yap; Chao Ping Hsu; Gernot Frenking; Tiow Gan Ong

doi:10.1021/jacs.7b08031

Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules

Wen Ching Chen, Wei Chih Shih, Titel Jurca, Lili Zhao, Diego M. Andrada, Chun Jung Peng, Chun Chi Chang, Shu Kai Liu, Yi Ping Wang, Yuh Sheng Wen, Glenn P.A. Yap, Chao Ping Hsu, Gernot Frenking, Tiow Gan Ong

School of Chemistry and Moleculai Engineering

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

66 Scopus citations

Abstract

An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).

Original language	English
Pages (from-to)	12830-12836
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	139
Issue number	36
DOIs	https://doi.org/10.1021/jacs.7b08031
State	Published - 13 Sep 2017

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Chen, W. C., Shih, W. C., Jurca, T., Zhao, L., Andrada, D. M., Peng, C. J., Chang, C. C., Liu, S. K., Wang, Y. P., Wen, Y. S., Yap, G. P. A., Hsu, C. P., Frenking, G., & Ong, T. G. (2017). Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules. Journal of the American Chemical Society, 139(36), 12830-12836. https://doi.org/10.1021/jacs.7b08031

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title = "Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules",

abstract = "An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).",

author = "Chen, {Wen Ching} and Shih, {Wei Chih} and Titel Jurca and Lili Zhao and Andrada, {Diego M.} and Peng, {Chun Jung} and Chang, {Chun Chi} and Liu, {Shu Kai} and Wang, {Yi Ping} and Wen, {Yuh Sheng} and Yap, {Glenn P.A.} and Hsu, {Chao Ping} and Gernot Frenking and Ong, {Tiow Gan}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = sep,

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doi = "10.1021/jacs.7b08031",

language = "英语",

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T2 - Unexpected π-Accepting Ability during Reactivity with Small Molecules

AU - Chen, Wen Ching

AU - Shih, Wei Chih

AU - Jurca, Titel

AU - Zhao, Lili

AU - Andrada, Diego M.

AU - Peng, Chun Jung

AU - Chang, Chun Chi

AU - Liu, Shu Kai

AU - Wang, Yi Ping

AU - Wen, Yuh Sheng

AU - Yap, Glenn P.A.

AU - Hsu, Chao Ping

AU - Frenking, Gernot

AU - Ong, Tiow Gan

PY - 2017/9/13

Y1 - 2017/9/13

N2 - An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).

AB - An investigation of carbodicarbenes, the less explored member of the carbenic complex/ligand family has yielded unexpected electronic features and concomitant reactivity. Observed 1,2-addition of E-H bonds (E = B, C, Si) across the carbone central carbon and that of the flanking N-heterocyclic carbene (NHC) fragment, combined with single-crystal X-ray studies of a model Pd complex strongly suggests a significant level of π-accepting ability at the central carbon of the NHC moiety. This feature is atypical of classic NHCs, which are strong σ-donors, with only nominal π-accepting ability. The unanticipated π-acidity is critical for engendering carbodicarbenes with reactivity more commonly observed with frustrated Lewis pairs (FLPs) rather than the more closely related NHCs and cyclic (alkyl)(amino)carbenes (CAACs).

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EP - 12836

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 36

ER -

Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules

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