title: 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.
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 N-O and N-N 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 V-N 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 N-O and N-N cleavage reactions.
authors.affiliation: School of Physical Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. Brian.Yates@utas.edu.au.
authors.forename: Robert
authors.initials: R
authors.lastname: Robinson
authors.affiliation: School of Physical Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. Brian.Yates@utas.edu.au.
authors.forename: Miranda F
authors.initials: MF
authors.lastname: Shaw
authors.affiliation: Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
authors.forename: Robert
authors.initials: R
authors.lastname: Stranger
authors.affiliation: School of Physical Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. Brian.Yates@utas.edu.au.
authors.forename: Brian F
authors.initials: BF
authors.lastname: Yates