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Theoretical study of the mechanism for the sequential NO and NN bond cleavage within N2O adducts of N-heterocyclic carbenes by a vanadium(III) complex

Citation

Robinson Jr, R and Shaw, MF and Stranger, R and Yates, BF, Theoretical study of the mechanism for the sequential N-O and N-N bond cleavage within N2O adducts of N-heterocyclic carbenes by a vanadium(III) complex, Dalton Transactions, 45, (3) pp. 1047-1054. ISSN 1477-9226 (2016) [Refereed Article]

Copyright Statement

Copyright 2016 The Royal Society of Chemistry

DOI: doi:10.1039/c5dt03600c

Abstract

A theoretical study into the reactions of the N2O adducts of N-heterocyclic carbenes (NHCs) and a V(III) complex was carried out using DFT calculations. Unlike most transition metal reactions with N2O that simply release N2 following O-atom transfer onto the metal centre, this NHC-based system traps the entire N2O molecule and then cleaves both the NO and NN bond in two consecutive reactions. The NHC presence increases the reactivity of N2O by altering the distribution of electron density away from the O-atom towards the two N-atoms. This electronic redistribution enables VN binding interactions to form a reactive N,O-donor intermediate species. Our results show that bond breaking with concomitant ligand migration occurs via a concerted process for both the NO and NN cleavage reactions.

Item Details

Item Type:Refereed Article
Keywords:small molecule activation
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Robinson Jr, R (Dr Robert Robinson)
Author:Shaw, MF (Miss Miranda Shaw)
Author:Yates, BF (Professor Brian Yates)
ID Code:106500
Year Published:2016
Funding Support:Australian Research Council (DP120101937)
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2016-02-12
Last Modified:2017-03-14
Downloads:0

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