Understanding the Importance of “Hydricity” in Enabling CO2 Reduction
Hydricity is defined as the free energy required to heterolytically cleave a metal-hydride bond, generating free hydride and a metal cation. This thermodynamic parameter is a critical predictor of metal-hydride-catalyzed CO2 to formic acid reduction. In particular, metal hydrides whose hydricity is less than 44 kcal/mol (the hydricity of formate in MeCN) are predicted to spontaneously react with CO2, while those with a hydricity greater than 44 kcal/mol will not. Thus, measuring the hydricity of a metal hydride is a key step in the design of CO2 reduction catalysts for use in developing fuels and carbon feedstocks. We have previously isolated examples of copper and silver hydride complexes, which have proven to be competent pre-catalysts for hydrosilylation reactions. To better understand the origins of group 11 hydride reactivity and to determine their efficacy as CO2 reduction catalysts, we endeavor to measure the hydricity of these complexes, as well develop a library of group 11 hydride complexes to explore the structure-function relationships of these materials.
Advisor: Trevor Hayton