EPR Spectroscopic Characterization of a Jahn-Teller Distorted (C3v→Cs) Four-Coordinate Chromium(V) Oxo Species

Article abstract of DOI:10.1002/ijch.201600036

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 distorted C_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 molecular g-values and ⁵³Cr and ¹⁷O hyperfine interactions. Analysis of density functional theory results and the g and 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.