On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]

Abstract

We report the experimental and computational investigations of the reactions of aryl, heteroaryl, and vinyl triflates with a model nickel(0) complex. While the reactions of most (hetero)aryl and vinyl triflates behave straightforwardly, the reactions of 2-pyridinyl triflates are rather different; under reaction conditions where the organotriflates are used in vast excess there is not a simple pseudo-first order behaviour. These reactions are further explored using DFT calculations, which show that both three- and five-centred oxidative addition transition states are viable, but that the experimentally-observed order of reactivity is not readily reproduced by considering a simple oxidative addition pathway.