Directing Group Strategy for the Isolation of Organoselenium(VI) Benzoselenonates: Metal-Free Catalysts for Hydrogen Evolution Reaction.

The exploration of fourth-period organoelements, particularly organoseleniums in their highest VI oxidation state, is limited owing to their stability and synthesis. Herein, the isolation of a new class of quinolinyl-embedded, hexavalent selenium(VI) benzoselenonates has been discussed and further evaluated for a metal-free electrocatalytic hydrogen evolution reaction (HER). The Se(VI) benzoselenonates exhibited high Faradaic efficiency (F.E.) of metal-free H 2 gas production up to 86% with a very good turnover number (TON) up to 43 and moderate overpotential (η) of 500 mV; in the presence of mild acetic acid source in a less deprotonating DMF solvent. Taken together with various (NMR, UV-vis, and EPR) spectroscopic and DFT computation studies, a plausible HER pathway is proposed, which suggests that the electrochemical reduction of quinolinyl ring is the initiation step and Se(VI) acts as the reaction site by involving a hydridic type of intermediate for the electrochemical H 2 gas generation.