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

doi:10.1002/ejic.200900252

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

Chemistry and Biochemistry

Research output: Contribution to journal › Article

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)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.

Original language	English (US)
Pages (from-to)	3414-3420
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	23
DOIs	https://doi.org/10.1002/ejic.200900252
State	Published - Aug 1 2009

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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., 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

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, 01.08.2009, p. 3414-3420.

Research output: Contribution to journal › Article

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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title = "Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases",

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.",

keywords = "Electrocatalysis, Enzyme catalysis, Hidrogenases, Iron, Ligand effects, Selenium, Substitution",

author = "Harb, {Mohammad K.} and Jochen Windhager and Daraosheh Ahmad and Helmar G{\"o}rls and Lockett, {L. Tori} and Noriko Okumura and Evans, {Dennis H.} and Glass, {Richard S.} and Lichtenberger, {Dennis L.} and Mohammad El-khateeb and Wolfgang Weigand",

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T1 - Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases

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

PY - 2009/8/1

Y1 - 2009/8/1

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.

KW - Electrocatalysis

KW - Enzyme catalysis

KW - Hidrogenases

KW - Iron

KW - Ligand effects

KW - Selenium

KW - Substitution

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U2 - 10.1002/ejic.200900252

DO - 10.1002/ejic.200900252

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10.1002/ejic.200900252