Nickel–Borolide Complexes and Their Complex Electronic Structure
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Borolides (BC42-) can be considered as dianionic heterocyclic analogues of monoanionic cyclopentadienides. Although both are formally six-π-electron donors, we herein demonstrate that the electronic structure of their corresponding transition metal complexes differs significantly, leading to altered properties. Specifically, the 18-electron sandwich complex Ni(iPr2NBC4Ph2)2 (1) features an ∼90° angle between the Ni-B-N planes and is best described as a combination of three limiting resonance structures with the major contribution stemming from a formally Ni2+ species bound to two monoanionic radical (BC4•-) ligands. Compound 1 displays two sequential one-electron oxidation events over a small potential range of <0.2 V, which strikingly contrasts the large potential separations between redox partners in the family of metallocenes, and the potential reasons for this unusual observation are discussed.
author list (cited authors)
Yruegas, S., Tang, H., Bornovski, G. Z., Su, X., Sung, S., Hall, M. B., Nippe, M., & Martin, C. D
complete list of authors
Yruegas, Sam||Tang, Hao||Bornovski, Gayle Z||Su, Xiaojun||Sung, Siyoung||Hall, Michael B||Nippe, Michael||Martin, Caleb D