Vanadyl is an attractive, earth-abundant first row transition metal oxidant, but could benefit from improved solubility in organic solvents and control of stereochemical outcome.  Outer-sphere ligand interactions in metal complexes are as important as direct metal-ligand interactions for applications such as catalysis. We have designed and synthesized a catechol-containing chelating ligand to bind vanadyl around the equatorial plane and interact with the axial oxygen via hydrogen bonds. The functional groups used in the ligand offer the potential for facile incorporation unto solid-phase support and potentially introduction of chiral centers close to the oxo functional group.  Additionally, our facile and modular synthetic approach enables the ligand structures to be altered without a complete overhaul of the synthetic plan. We are studying the ligand-vanadyl complex electrochemically in organic solvents to determine chelation effects on vanadyl redox potentials. By chelating the vanadyl oxo ligand, the electrochemistry of the resulting complex can be adjusted, demonstrating a novel approach for mild homogeneous oxidation of small organic molecules using vanadyl, similar to traditional Dess-Martin periodinane chemistry. Through careful ligand design considerations, our ligand scaffold may provide another mild organic soluble oxidant for organic chemists to employ in their chemistry toolbox.

Designing a ligand scaffold to chelate vanadyl for use as a mild oxidant

ACS Fall 2021

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