Unraveling the catalytic mechanisms of H₂ production with thiosemicarbazone nickel complexes.

ABSTRACT: Thiosemicarbazone-based complexes have been explored as a new class of redox-active catalysts H₂ production due to their flexibility for extensive optimization. To rationalize the process, we need to understand how these complexes function. In this work, we used DFT calculations to investigate the various mechanisms that could take place for three previously characterized Ni complexes. We found that two possible mechanisms are compatible with previously published experimental data, involving protonation of two adjacent N atoms close to the metal center. The first step likely involves a proton-coupled electron transfer process from a proton source to one of the distal N atoms in the ligand. From here, a second proton can be transferred either to the coordinating N atom situated i

SUBMITTER: Barrozo A 

PROVIDER: S-EPMC8694661 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature