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

journal contribution
posted on 2023-05-17, 11:14 authored by Alireza AriafardAlireza Ariafard, Zarkoob, F, Batebi, H, Stranger, R, Brian YatesBrian Yates
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.

Funding

Australian Research Council

History

Publication title

Organometallics

Volume

30

Issue

22

Pagination

6218-6224

ISSN

0276-7333

Department/School

School of Natural Sciences

Publisher

American Chemical Society

Place of publication

Washington, USA

Rights statement

Copyright 2011 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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