Formate dehydrogenases catalyze the final step of the oxidation of C1 substrates to CO2 in methylotrophic organisms. Currently, a widely cited mechanism involves orthogonal proton-electron transfer mediated by a tungsten or molybdenum sulfido ligand. Capitalizing on synthetic work by Holm and coworkers, we have determined the hydricity of a model complex of these active sites in order to gain insight into the mechanism of this transformation. DFT calculations and IR spectroscopy of one of these complexes suggest that the site of protonation on the reduced species is on the tungsten center rather than the terminal sulfido ligand. Further work includes the determination of the hydricity and site of protonation of related model complexes.

Determining the site of protonation and the hydricity of active-site model complexes of the tungsten- and molybdenum-containing formate dehydrogenases

2019 Fall National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.