Kinetics of chromium(V)-oxo and chromium(IV)-oxo porphyrins: Reactivity and mechanism for sulfoxidation reactions

Skipworth, Tristan; Khashimov, Mardan; Ojo, Iyanu; Zhang, Rui

doi:10.1016/j.jinorgbio.2022.112006

Abstract

Metal‐oxo coordination compounds have garnered significant interest over the years. The reactivity of the metal‐oxo bond is governed by the geometry, charge, spin state, and identity of the other ligands. In this report, we characterize a distortedC_3v‐symmetric Cr^V‐oxo complex that has unique magnetic properties, compared with all other known chromyl species. Continuous wave and pulse electron paramagnetic resonance were used to measure the molecularg‐values and⁵³Cr and¹⁷O hyperfine interactions. Analysis of density functional theory results and thegand hyperfine tensors, in the context of a crystallographically observed Jahn‐Teller distortion, suggests an electronic structure that results from the mixing of two sets of doubly degenerate orbital states. This mixing is only made possible by the approximate three‐fold symmetry of the ligand set.

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