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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 higher and overpotential much lower than its precursor bis-iron hexacarbonyl model which is active in its Fe(0)-Fe(0) state. The formation of a terminal Fe-H species, evidenced by spectroelectrochemistry in organic solvent, via a rate determining proton coupled electron transfer step and protonation of the adjacent azadithiolate, lowers the kinetic barrier leading to diffusion controlled rates of H₂ evolution. The stereo-electronic factors enhance its catalytic rate by 3 order of magnitude relative to a bis-iron hexacarbonyl precursor at the same pH and potential.

SUBMITTER: Nayek A

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

REPOSITORIES: biostudies-literature

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

Nayek Abhijit A Dey Subal S Patra Suman S Rana Atanu A Serrano Pauline N PN George Simon J SJ Cramer Stephen P SP Ghosh Dey Somdatta S Dey Abhishek A

Chemical science 20240101 6

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<s ...[more]

PMID: 38332837

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Dataset Information

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

Publications

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

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