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 | |
| State | Published - Aug 2009 |
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Keywords
- Electrocatalysis
- Enzyme catalysis
- Hidrogenases
- Iron
- Ligand effects
- Selenium
- Substitution
ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
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 journal › Article
}
TY - JOUR
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
Y1 - 2009/8
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
UR - http://www.scopus.com/inward/record.url?scp=68249114746&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=68249114746&partnerID=8YFLogxK
U2 - 10.1002/ejic.200900252
DO - 10.1002/ejic.200900252
M3 - Article
AN - SCOPUS:68249114746
SP - 3414
EP - 3420
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
IS - 23
ER -