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Understanding the influence of donor-acceptor diazo compounds on the catalyst efficiency of B(C6F5)3 towards carbene formation


Babaahmadi, R and Dasgupta, A and Hyland, CJT and Yates, BF and Melen, RL and Ariafard, A, Understanding the influence of donor-acceptor diazo compounds on the catalyst efficiency of B(C6F5)3 towards carbene formation, Chemistry - A European Journal, 28, (11) Article e202104376. ISSN 0947-6539 (2022) [Refereed Article]

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2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution 4.0 International (CC BY 4.0) License, ( which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

DOI: doi:10.1002/chem.202104376


Diazo compounds have been largely used as carbene precursors for carbene transfer reactions in a variety of functionalization reactions. However, the ease of carbene generation from the corresponding diazo compounds depends upon the electron donating/withdrawing substituents either side of the diazo functionality. These groups strongly impact the ease of N2 release. Recently, tris(pentafluorophenyl)borane [B(C6F5)3] has been shown to be an alternative transition metal-free catalyst for carbene transfer reactions. Herein, a density functional theory (DFT) study on the generation of carbene species from α-aryl α-diazocarbonyl compounds using catalytic amounts of B(C6F5)3 is reported. The significant finding is that the efficiency of the catalyst depends directly on the nature of the substituents on both the aryl ring and the carbonyl group of the substrate. In some cases, the boron catalyst has negligible effect on the ease of the carbene formation, while in other cases there is a dramatic reduction in the activation energy of the reaction. This direct dependence is not commonly observed in catalysis and this finding opens the way for intelligent design of this and other similar catalytic reactions.

Item Details

Item Type:Refereed Article
Keywords:borane catalysis, DFT calculations, diazo compounds
Research Division:Chemical Sciences
Research Group:Physical chemistry
Research Field:Catalysis and mechanisms of reactions
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Babaahmadi, R (Mr Rasool Babaahmadi)
UTAS Author:Yates, BF (Professor Brian Yates)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:150057
Year Published:2022
Funding Support:Australian Research Council (DP180100904)
Web of Science® Times Cited:4
Deposited By:College Office - CoSE
Deposited On:2022-05-16
Last Modified:2022-10-27
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