A computational investigation of the thermodynamics and kinetics of multiple single-step electron transfers of various Ni- and chalcogen-containing complexes

Abstract

Continued increase in green house gas emissions will lead to irreversible and unpredictable damage to the environment and biosphere. CO2 alone contributes to about two-thirds of the energy imbalance causing climate change. The bulk of these CO2 emissions can be traced to fossil fuels, which presently account for 82% of this green house gas. Developing effective renewable–alternative fuel sources is crucial to mitigate the harmful effects of fossil fuels. One such alternative fuel source is molecular hydrogen, which can be produced by the photocatalytic splitting of water using metal-based catalysts. This study investigates the thermodynamics and kinetics associated with single-step protonations and reductions of Ni[(S2C2H2)(N2C2H4)], Ni[(Se2C2H2)(N2C2H4)], and Ni[(Te2C2H2)(N2C2H4)] complexes using density functional theory. Results found diselenolene to be the least endergonic for the formation of the triply reduced, doubly protonated species with a Gibbs protonation energy of 79.6 kJ mol−1. Ditellurolene and dithiolene were slightly more endergonic with Gibbs protonation energies of 87.7 and 91.6 kJ mol−1, respectively. The most thermodynamically favorable pathways were found to be the ECCEE pathway for dithiolene and diselenolene, whereas the CECEE mechanism was found to be most favorable for ditellurolene. Kinetically, it was found that there were two feasible pathways for all three complexes. The first was a CCEEE pathway and the second was a CECEE pathway. All complexes were found to have similar Gibbs activation energies.