Cyclic Voltammetric Studies of Chlorine-Substituted Diiron Benzenedithiolato Hexacarbonyl Electrocatalysts Inspired by the [FeFe]-Hydrogenase Active Site

Elizabeth S. Donovan, Joseph J. McCormick, Gary S. Nichol, Greg A. N. Felton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Chlorine-substituted benzenedithiols have been coordinated to iron carbonyl to yield a series of hydrogen-producing electrocatalysts: [Fe2(μ-S2C6H4-xClx)(CO)6], where x = 0, 2-4, and [Fe2(μ-S2C6H3Me)(CO)6]. Among this series the novel compounds [Fe2(μ-S2C6Cl3H)(CO)6] (4) and [Fe2(μ-S2C6Cl4)(CO)6] (5) have been characterized by X-ray crystallography. IR spectroscopy and electrochemical analysis were used to evaluate the electronic structure of these proton-reducing molecular electrocatalysts. The increase in the number of electron-withdrawing groups upon the electrocatalyst leads to an anodic shift in reduction potential and a concomitant lowering of the overpotential of hydrogen evolution. An overpotential of just 0.39 V is observed for 5 with acetic acid (pKa = 22.3 in acetonitrile).

Original languageEnglish
Pages (from-to)8067-8070
Number of pages4
JournalOrganometallics
Volume31
Issue number23
Early online date12 Nov 2012
DOIs
Publication statusPublished - 10 Dec 2012

Keywords

  • X-RAY STRUCTURES
  • HYDROGEN GENERATION
  • PROTON REDUCTION
  • METAL-COMPLEXES
  • BENZENE-1,2-DITHIOLATE LIGAND
  • 2-ELECTRON REDUCTION
  • BINUCLEAR IRON(I)
  • ELECTROCHEMISTRY
  • CATALYSIS
  • ELECTRON

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