Substrate coordination and activation at a bis(N-heterocyclic carbene)nickel(0) fragment incorporating a siloxane linker
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2019-08-27
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Abstract
This work hones in on the synthesis and reactivity of a novel bis(NHC)Ni0 fragment in pursuit of expanding the underexplored family of chelating bis(NHC) ligands in the stabilization of low-valent species. Contrasting current literature, which standardizes rigid and constraining ligand designs, our strategy employed a flexible ligand capable of accommodating a wide range of bite angles. Herein, the stoichiometric reactions of a novel chelated Ni0 complex are reported. Combination of bis(NHC)Ni0 with the main group fragments GeCl2 and P4 yielded non-traditional bonding scenarios with Ni0, which represent reactive intermediates along the path to oxidative addition. The archetypal Lewis acid, tris(pentafluorophenyl)borane was activated by Lewis basic bis(NHC)Ni0. This represents the first report of C-F cleavage of B(C6F5)3 by a transition metal. A redox event hosted by a nickel substituted borane complex was useful in tuning its Lewis acidity. Bolstering the representation of bis(NHC) ligands in the stabilization of Ni0, these studies provide insight into the reactivity of ligand designs that alter bite angles while unveiling electronic nuance important in oxidative addition reactions with low-valent group 10 transition metals.
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Gendy, C. (2019). Substrate coordination and activation at a bis(N-heterocyclic carbene)nickel(0) fragment incorporating a siloxane linker (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.