Synthetic polynuclear clusters capable of undergoing multielectron processes are of interest both for their relevance to understanding polynuclear reaction sites in nature and for their potential to achieve novel transformations of small molecule substrates. The multielectron capacity of first-row transition metal clusters previously synthesized by our group can be expanded by incorporating earlier transition metals into the clusters or by loading them with additional electrons via reduction. The former strategy gives rise to a trichromium cluster with expanded redox capacity as well as increased structural flexibility and the ability to switch between redox-delocalized and site-isolated reactivity using solvent control. The latter strategy results in a dramatic reorganization and change in electronic structure to provide delocalized mixed-valent anionic trinuclear clusters of iron, manganese, cobalt, and nickel.

Multielectron reactivity and electronic structure of first-row transition metal trinuclear complexes

254th National Meeting (2017)

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