Scrutinizing formally NiIV centers through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory

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Abstract

Nickel K- and L2,3-edge X-ray absorption spectra (XAS) are discussed for 16 complexes and complex ions with nickel centers spanning a range of formal oxidation states from II to IV. K-edge XAS alone is shown to be an ambiguous metric of physical oxidation state for these Ni complexes. Meanwhile, L2,3-edge XAS reveals that the physical d-counts of the formally NiIV compounds measured lie well above the d6 count implied by the oxidation state formalism. The generality of this phenomenon is explored computationally by scrutinizing 8 additional complexes. The extreme case of NiF62− is considered using high-level molecular orbital approaches as well as advanced valence bond methods. The emergent electronic structure picture reveals that even highly electronegative F-donors are incapable of supporting a physical d6 NiIV center. The reactivity of NiIV complexes is then discussed, highlighting the dominant role of the ligands in this chemistry over that of the metal centers.

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DiMucci, I. M., Titus, C. J., Nordlund, D., Bour, J. R., Chong, E., Grigas, D. P., … Lancaster, K. M. (2023). Scrutinizing formally NiIV centers through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory. Chemical Science, 14(25), 6915–6929. https://doi.org/10.1039/d3sc02001k

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