Abstract
The cobalt(III) macrocyclic Schiff-base complex, [Co III(CR)Cl]ClO 4 (CR = 2,12-dimethyl-3,7,11,17-tetra-azabicyclo[11.3.1]-heptadeca-1(17),2,11,13,15-pentaene), is an active catalyst for the electrocatalytic proton reduction to generate dihydrogen in both acetonitrile and 100% aqueous solution (at −0.57 and −0.85 V vs SCE, respectively), using p-cyanoanilinium tetrafluoroborate and acetic acid as proton sources, respectively. Bulk electrolysis confirmed that dihydrogen is produced with >90% Faradaic yields and >50 TON in both solvents. [Co III(CR)Cl 2]ClO 4 also catalyzes photo-driven ( λ > 390 nm) hydrogen production in aqueous acetonitrile at TON of 180 (not optimized), using [Ir III(ppy) 2(bpy)]PF 6 as the photosensitizer, triethanolamine (TEOA) as the sacrificial donor and acetic acid as the proton source.
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