Water oxidation catalyzed by a molecular catalyst is a challenging chemical reaction – improving catalyst speed and especially durability present ongoing challenges. Catalysts of the family [(terpy)(bipy)Ru(H2O)]2+ have proven a fruitful site of inquiry given their well-studied mechanistic behavior and good catalytic performance. Recent work by the group of Thummel has found that addition of a carboxylate pendant base significantly improved catalyst performance. Our study concerns pendant bases containing non-carbon atoms. In this study, we report the effect of heteroatom pendant bases on water oxidation in the context of [(terpy)(bipy)Ru(L)]n+ catalyst motif. We also investigated the effects of substituting the atom directly bound to the ruthenium center. Thus, we incorporated more strongly σ donating ligands by substituting carbon for nitrogen at the donor site. The goal of this modification is to stabilize proposed catalytic intermediates and promote rapid formation of dioxygen. The synthesis, characterization, and catalytic performance these compounds will be discussed with specific reference to the effect of carbon/nitrogen substitution and its interplay with pendant base.

Strongly σ-donating ligands with pendant bases for water oxidation catalysis

2019 Fall National Meeting

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