First insights into the protonation of dissymetrically disubstituted di-iron azadithiolate models of the [FeFe]H2ases active site

Abstract

Dissymetrically disubstituted di-iron azadithiolate complexes [Fe₂(CO)₄(κ²-LL){μ-SCH₂N(ⁱPr)CH₂S}] (LL = dppe, phen) protonate exclusively at the N atom of the bridge, like the hexacarbonyl precursor but in contrast to symmetrically disubstituted analogues; substitution of dppe for two CO groups noticeably increases the kinetics of the electrocatalytic proton reduction process.