While exploring the chemistry of low-coordinate, low-valent nickel complexes, we sought (N-heterocyclic carbene)-supported nickel(I) alkoxides as synthetic intermediates. Initial efforts yielded ill-defined materials that more or less behaved as if they were, or at least contained, the desired species. Some synthetic refinement afforded a well-defined nickel(I) alkoxide dimer. This paramagnetic (<i>S</i> = 1) complex undergoes alkoxide abstraction by a suitable Lewis acid to afford either an alkoxy-bridged dinickel(I) cation, also <i>S</i> = 1, or the nickel(I) triflate depending on the conditions chosen. Each of these structurally characterized complexes serves as a platform for the synthesis of new nickel–nickel or nickel–heteroatom bonds.

Nickel(I) alkoxides as synthons for nickel element and nickel-nickel bonds

ACS Fall 2021

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