We have had a long-standing interest in designing new catalysts for CO2 reduction using earth abundant first row metals. Several strategies can be using to control the coordination sphere as becomes important with first row metals that tend to have rapid ligand exchange rates. With CNC pincer ligands it becomes important to avoid the formation of octahedral bis ligand complexes of the type (CNC)2M. One strategy is to use low valent first row metals. These metals prefer to be four or five coordinate and thus bis ligand complexes are avoided. A second strategy is via the protection of the coordination sphere with steric encumbrance. Third, by increasing the denticity of the ligand, free sites for catalysis are also protected. Principally, our results will focus on the use of cobalt and nickel with these three strategies for the formation of catalysts for light driven CO2 reduction.

First row transition metal photocatalysts for CO2 reduction: Control of the coordination environment

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ACS Fall 2022

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