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Assembly and Redox-Rich Hydride Chemistry of an Asymmetric Mo2S2 Platform
Alex McSkimming1, Jordan W Taylor1, W Hill Harman1
1Department of Chemistry, University of California, Riverside, California, CA 92521, USA.
Abstract:
Although molybdenum sulfide materials show promise as electrocatalysts for proton reduction, the hydrido species proposed as intermediates remain poorly characterized. We report herein the synthesis, reactions and spectroscopic properties of a molybdenum-hydride complex featuring an asymmetric Mo2S2 core. This molecule displays rich redox chemistry with electrochemical couples at E½ = -0.45, -0.78 and -1.99 V vs. Fc/Fc+. The corresponding hydrido-complexes for all three redox levels were isolated and characterized crystallographically. Through an analysis of solid-state bond metrics and DFT calculations, we show that the electron-transfer processes for the two more positive couples are centered predominantly on the pyridinediimine supporting ligand, whereas for the most negative couple electron-transfer is mostly Mo-localized.
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