Facile electrocatalytic proton reduction by a [Fe-Fe]-hydrogenase bio-inspired synthetic model bearing a terminal CN^- ligand.

ABSTRACT: An azadithiolate bridged CN^- bound pentacarbonyl bis-iron complex, mimicking the active site of [Fe-Fe] H₂ase is synthesized. The geometric and electronic structure of this complex is elucidated using a combination of EXAFS analysis, infrared and Mössbauer spectroscopy and DFT calculations. The electrochemical investigations show that complex 1 effectively reduces H⁺ to H₂ between pH 0-3 at diffusion-controlled rates (10¹¹ M^-1 s^-1) i.e. 10⁸ s^-1 at pH 3 with an overpotential of 140 mV. Electrochemical analysis and DFT calculations suggests that a CN^- ligand increases the pK_a of the cluster enabling hydrogen production from its Fe(i)-Fe(0) state at pHs much h

SUBMITTER: Nayek A 

PROVIDER: S-EPMC10848691 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature