Coordination compounds featuring terminal oxo (O2-) ligands bonded to first-row transition metals are important synthetic targets that are implicated in many powerful chemical transformations (e.g. biological and electrocatalytic water oxidation). Although expected to exhibit a vast range of valuable reactivity, practical utilization of such mid- and late-metal complexes is precluded by the limited or non-existent of array characterized examples and the absence of suitably descriptive and predictive models that would facilitate their synthesis and isolation. Drawing predictions from molecular orbital theory, the electronic structure elements expected to stabilize these complexes are derived and serve as guiding principles for the design of novel ligand scaffolds. With the aim of identifying and evaluating the relative contributions of factors affecting metal-oxo stability and reactivity, we have developed a series of trianionic, tripodal ligands as promising candidates. Results following from the synthesis of first-row transition-metal complexes with our initially developed ligand designs are presented.

Trianionic tripodal ligands: Progress toward terminal oxo compounds of the first-row metals

245th National Meeting (2013)

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