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Electron-Transfer-Catalyzed Rearrangement of Unsymmetrically Substituted Diiron Dithiolate Complexes Related to the Active Site of the [FeFe]-Hydrogenases
- Source :
- Inorganic Chemistry, Inorganic Chemistry, American Chemical Society, 2007, 46 (23), pp.9863-9872. ⟨10.1021/ic701327w⟩
- Publication Year :
- 2007
- Publisher :
- American Chemical Society (ACS), 2007.
-
Abstract
- International audience; Novel asymmetrically substituted azadithiolate compounds [Fe2(CO)4(κ2-dppe){μ-SCH2N(R)CH2S}] (R = iPr, 1a; CH2CH2OCH3, 1b; CH2C6H5, 1c) have been synthesized by treatment of [Fe2(CO)6(μ-adt)] [adt = SCH2N(R)CH2S, with R = iPr, CH2CH2OCH3, CH2C6H5] with dppe (dppe = Ph2PCH2CH2PPh2) in refluxing toluene in the presence of Me3NO. 1a−c have been characterized by single-crystal X-ray diffraction analyses. The electrochemical investigation of 1a−c and of [Fe2(CO)4(κ2-dppe)(μ-pdt)] (1d) [pdt = S(CH2)3S] in MeCN− and THF−[NBu4][PF6] has demonstrated that the electrochemical reduction of 1a−d gives rise to an Electron-transfer-catalyzed (ETC) isomerization to the symmetrical isomers 2a−d where the dppe ligand bridges the iron centers. Compounds 2a−d were characterized by IR and NMR spectroscopy, elemental analysis, and X-ray crystallography for 2a.
- Subjects :
- Iron-Sulfur Proteins
Models, Molecular
Spectrophotometry, Infrared
Stereochemistry
Crystallography, X-Ray
010402 general chemistry
Electrochemistry
Ferric Compounds
01 natural sciences
Medicinal chemistry
Catalysis
Electron Transport
Inorganic Chemistry
Electron transfer
chemistry.chemical_compound
Hydrogenase
[CHIM]Chemical Sciences
Sulfhydryl Compounds
Physical and Theoretical Chemistry
Nuclear Magnetic Resonance, Biomolecular
Binding Sites
biology
010405 organic chemistry
Chemistry
Ligand
Active site
Nuclear magnetic resonance spectroscopy
Toluene
0104 chemical sciences
biology.protein
Isomerization
Subjects
Details
- ISSN :
- 1520510X and 00201669
- Volume :
- 46
- Database :
- OpenAIRE
- Journal :
- Inorganic Chemistry
- Accession number :
- edsair.doi.dedup.....7771ed28c2ae234176ce51f6130e3d9e