Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases

Mohammad K. Harb, Jochen Windhager, Daraosheh Ahmad, Helmar Görls, L. Tori Lockett, Noriko Okumura, Dennis H. Evans, Richard S. Glass, Dennis L. Lichtenberger, Mohammad El-khateeb, Wolfgang Weigand

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41 Scopus citations

Abstract

The displacement of terminal CO ligands in Fe2(μSe 2C3H5CH3)(CO)6 (1) by triphenylphosphane, trimethyl phosphite, and bis(diphenylphosphanyl)ethane (dppe) li:jands is investigated. Treatment of 1 with 1. equiv. of triphenylphosphane afforded Fe2(μ-Se2C3H 5CH3)(CO)5(PPh3) (2). The mono- and disubstituted phosphite complexes Fe2(μSe2C 3H5CH3)(CO)5P(OMe)3(3) and Fe2(μ-Se2C3H5CH 3)(CO)4-[P(OMe)3]2 (4) were obtained from the reaction of 1 with excess P(OMe)3 at reflux in toluene. In contrast, the reaction of 1 with 1 equiv. of dppe in the presence of Me 3NO-2H2O gave a mixture of Fe2(μ-Se 2C3H5CH3)(CO)42-dppe) (5) and [Fe2(μ-Se2C 3H5CH3)(CO)5]2(μ-dppe) (6). The newly synthesized complexes 2-6 were fully characterized by IR, 1H NMR, 13C NMR, 77Se{1H} NMR, and 31P{1H} NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction analysis. Complex 2 has proved to be a catalyst for the electrochemical reduction of the weak acid, acetic acid, to give molecular hydrogen.

Original languageEnglish (US)
Pages (from-to)3414-3420
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number23
DOIs
StatePublished - Aug 1 2009

Keywords

  • Electrocatalysis
  • Enzyme catalysis
  • Hidrogenases
  • Iron
  • Ligand effects
  • Selenium
  • Substitution

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Harb, M. K., Windhager, J., Ahmad, D., Görls, H., Lockett, L. T., Okumura, N., Evans, D. H., Glass, R. S., Lichtenberger, D. L., El-khateeb, M., & Weigand, W. (2009). Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases. European Journal of Inorganic Chemistry, (23), 3414-3420. https://doi.org/10.1002/ejic.200900252