Ammonia Activation by a Nickel NCN-Pincer Complex featuring a Non-Innocent N-Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium
Brown, R., Garcia, J., Valjus, J., Roberts, C., Tuononen, H., Parvez, M., & Roesler, R. (2015). Ammonia Activation by a Nickel NCN-Pincer Complex featuring a Non-Innocent N-Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium. Angewandte Chemie International Edition, 54 (21), 6274-6277. doi:10.1002/anie.201500453
Published inAngewandte Chemie International Edition
© 2015 Wiley-VCH Verlag GmbH & Co. This is a final draft version of an article whose final and definitive form has been published by Wiley. Published in this repository with the kind permission of the publisher.
A Ni0-NCN pincer complex featuring a six-membered N-heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square-planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni0 complex rapidly activated ammonia at room temperature, in a ligand-assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent-dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non-innocent behavior of the NHC ligand.