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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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 2009

Fingerprint

phosphine
Phosphites
Hydrogenase
Carbon Monoxide
Ethane
trimethyl phosphite
Nuclear magnetic resonance
Toluene
Acetic Acid
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Hydrogen

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Harb, M. K., Windhager, J., Ahmad, D., Görls, H., Lockett, L. T., Okumura, N., ... 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

Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases. / Harb, Mohammad K.; Windhager, Jochen; Ahmad, Daraosheh; Görls, Helmar; Lockett, L. Tori; Okumura, Noriko; Evans, Dennis H.; Glass, Richard S; Lichtenberger, Dennis L; El-khateeb, Mohammad; Weigand, Wolfgang.

In: European Journal of Inorganic Chemistry, No. 23, 08.2009, p. 3414-3420.

Research output: Contribution to journalArticle

Harb, MK, Windhager, J, Ahmad, D, Görls, H, Lockett, LT, Okumura, N, Evans, DH, Glass, RS, Lichtenberger, DL, El-khateeb, M & Weigand, W 2009, 'Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases', European Journal of Inorganic Chemistry, no. 23, pp. 3414-3420. https://doi.org/10.1002/ejic.200900252
Harb, Mohammad K. ; Windhager, Jochen ; Ahmad, Daraosheh ; Görls, Helmar ; Lockett, L. Tori ; Okumura, Noriko ; Evans, Dennis H. ; Glass, Richard S ; Lichtenberger, Dennis L ; El-khateeb, Mohammad ; Weigand, Wolfgang. / Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases. In: European Journal of Inorganic Chemistry. 2009 ; No. 23. pp. 3414-3420.
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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)4(κ 2-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.",
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AU - Harb, Mohammad K.

AU - Windhager, Jochen

AU - Ahmad, Daraosheh

AU - Görls, Helmar

AU - Lockett, L. Tori

AU - Okumura, Noriko

AU - Evans, Dennis H.

AU - Glass, Richard S

AU - Lichtenberger, Dennis L

AU - El-khateeb, Mohammad

AU - Weigand, Wolfgang

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N2 - 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)4(κ 2-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.

AB - 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)4(κ 2-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.

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KW - Enzyme catalysis

KW - Hidrogenases

KW - Iron

KW - Ligand effects

KW - Selenium

KW - Substitution

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