Transition Metal Oxo Complexes with Unusual Electronic Structures
Transition metal oxo complexes play critical roles throughout synthetic and natural systems. Among the varied reactivity of oxo complexes, the importance of radical reactivity is a theme that spans much of the chemistry of these species. Indeed, radical pathways have been proposed for epoxidation, hydroxylation, and even O-O bond formation processes mediated by transition metal oxo complexes.
Although there are some classic electronic structures that lead to this radical reactivity, such as the role of S =1 Fe=O complexes in hydroxylation, there has been a surge of interest in altering these classic electronic structures to more fully understand and control the reactivity of these species. One such change has been shifting from tetragonal symmetry to trigonal symmetry, typically with trigonal bipyramidal complexes. This project will diverge from these examples by pursuing two strategies: 1) by pursuing lower coordinate oxo-complexes, such as those found in pseudo-tetrahedral geometries and 2) by developing oxygen rich ligand scaffolds to favor high-spin states.