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DFT Studies on the Carboxylation of the C−H Bond of Heteroarenes by Copper(I) Complexes


Ariafard, A and Zarkoob, F and Batebi, H and Stranger, R and Yates, BF, DFT Studies on the Carboxylation of the C−H Bond of Heteroarenes by Copper(I) Complexes, Organometallics, 30, (22) pp. 6218-6224. ISSN 0276-7333 (2011) [Refereed Article]

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Copyright Statement

Copyright 2011 American Chemical Society

DOI: doi:10.1021/om200744a


In this study, we have used density functional theory to identify a new mechanism for the formation of carboxylate compounds from heteroarenes, such as benzoxazole, in the presence of copper catalysts. This new mechanism involves the formation of a carbene intermediate that is indirectly stabilized by the electron-releasing copper. This intermediate carbene can isomerize to the experimentally observed resting state of the catalytic cycle, but it is the intermediate carbene itself that has the greater reactivity toward CO2 and that leads to the final carboxylate product via a lower-energy pathway. Our findings demonstrate the importance of considering metal-stabilized carbenes in such reactions. Our findings also suggest that this carbene intermediate can act as a nucleophile in other organometallic reactions.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Theoretical and computational chemistry
Research Field:Theoretical quantum chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:76879
Year Published:2011
Funding Support:Australian Research Council (DP0986529)
Web of Science® Times Cited:36
Deposited By:Chemistry
Deposited On:2012-03-14
Last Modified:2017-10-06

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