How Metal Nuclearity Impacts Electrocatalytic H2 Production in Thiocarbohydrazone-based Complexes
Abstract
Thiocarbohydrazone-based catalysts feature ligands that are potentially electrochemically active. From the synthesis point of view, these ligands can be easily tailored, opening multiple strategies for optimization, such as using different substituent groups or metal substitution. In this work, we show the possibility of a new strategy, involving nuclearity of the system, meaning different number of metal centers. We report the synthesis and characterization of a trinuclear nickel-thiocarbohydrazone complex displaying an improved turnover rate compared to its mononuclear counterpart. We use DFT calculations to show that the mechanism involved is metal-centered, unlike the metal-assisted ligand-centered mechanism found in the mononuclear complex. Finally, we show that two possible mechanisms can be assigned to this catalyst, all involving an initial double reduction of the system.
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