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 › peer-review

44 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

Keywords

Electrocatalysis
Enzyme catalysis
Hidrogenases
Iron
Ligand effects
Selenium
Substitution

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.200900252

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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 › peer-review

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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doi = "10.1002/ejic.200900252",

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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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DO - 10.1002/ejic.200900252

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