Molecular catalysis for H2 production and uptake: understanding the basis of reversibility in bioinspired catalysts

A thorough analytical treatment allows determining all thermodynamic and kinetic parameters of reversible electrocatalytic oxidation and production of dihydrogen mediated by the molecular DuBois/Shaw nickel bisdiphosphine complexes bearing pendant bases. This analysis shed light on the key activity descriptors responsible for reversible vs. bidirectional catalysis and paves the way towards rational optimization of such molecular catalysts.