The Verani and Schlegel groups have been partners in the development of groundbreaking work toward the design of new architectures based on earth-abundant transition metals and capable of water splitting. The work prioritizes the design of manganese, iron, cobalt and ruthenium species with new ligands, the understanding of their electronic and electrochemical behavior and their testing toward water oxidation and proton reduction. In this symposium we will focus on the current efforts on proton-reduction, as follows: (i) the work of Basu (experiment) and Allard (calculations) on the effect of ligand substitution on the overpotential of cobalt complexes with electroactive phenolate-rich [N2O3] donor type ligands, where appropriate substituents on phenylenediamine or phenolate moieties decrease the Co-based potentials; (ii) the work of Basu (experiment) and Shi (calculations) on the energetics of axial ligand dissociation in cobalt oximes, where we reexamine the order of redox vs. chemical events leading to the catalytic Co(I) species; (iii) the work of Basu (experiment) and Mazunder (calculations) on the chemical conversions (=O and �OH insertion) of a cobalt complex with a new pendant-arm [N2N'3] polypyridyl ligand, where we observe that amines yield imines and amides unless a methyl protective group is used. Interestingly, all species show some degree of catalytic activity. Time permitting, we will also discuss progress toward the synthesis and electronic characterization of heterobinuclear ruthenium/cobalt systems. Funding DOE-BES DE-SC0001907

Concerted efforts toward new cobalt-based catalysts for proton reduction

248th National Meeting (2014)

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