Electrocatalytic HER Performance of [FeFe]‐Hydrogenase Mimics Bearing M‐salen Moieties (M=Zn, Ni, Fe, Mn)
Year: 2024
Type: article
Abstract: The synthesis and characterization of novel compounds (5‐8) as mimetics of [FeFe]‐hydrogenase, combining two distinct systems capable of participating in hydrogen evolution reactions (HER): the [(μ‐adt)Fe2(CO)6] fragment and M‐salen complexes (salen=N,N′‐bis(salicylidene)ethylenediamine) (M=Zn, Ni, Fe, Mn), is reported. These complexes were synthesized in high yields via a three‐step procedure from N,N′‐bis(4‐R‐salicylidene)ethanediamine) 4 [R=Fe2(CO)6(μ‐SCH2)2NCOCH2O]. Structural analysis through spectroscopic, spectrometric, and computational (DFT) methods confirmed distorted tetrahedral and square‐planar geometries for Zn‐salen and Ni‐salen complexes (5 and 6) respectively, while complexes Fe‐salen 7 and Mn‐salen 8 exhibit square‐based pyramidal structures typical of Fe(III) and Mn(III) high‐spin salen‐complexes. Electrochemical studies revealed different reduction events for [(μ‐adt)Fe2(CO)6] and M‐salen moieties, but the electrocatalytic experiments in TFA demonstrated a clear cooperative effect between these components, especially at higher acid concentrations. Notably, the Ni‐salen (6), Fe‐salen (7), and Mn‐salen (8) complexes exhibit significant reductions in overpotential, highlighting their potential for enhanced catalytic performance.
Source: Chemistry - A European Journal
Authors: Sergio Aguado, Mar Gómez‐Gallego, Luis Casarrubios, Miguel A. Sierra
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
OpenAlex ID: W4405707972