title: Electron-transfer-catalyzed rearrangement of unsymmetrically substituted diiron dithiolate complexes related to the active site of the [FeFe]-hydrogenases.
abstract: Novel asymmetrically substituted azadithiolate compounds [Fe2(CO)4(kappa2-dppe){micro-SCH2N(R)CH2S}] (R=iPr, 1a; CH2CH2OCH3, 1b; CH2C6H5, 1c) have been synthesized by treatment of [Fe2(CO)6(micro-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(kappa2-dppe)(micro-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.
authors.affiliation: UMR CNRS 6521, Chimie, Electrochimie Moléculaires et Chimie Analytique, UFR Sciences et Techniques, Université de Bretagne Occidentale, CS 93837, 29238 Brest-Cedex 3, France.
authors.forename: Salah
authors.initials: S
authors.lastname: Ezzaher
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Capon
authors.forename: Frédéric
authors.initials: F
authors.lastname: Gloaguen
authors.forename: François Y
authors.initials: FY
authors.lastname: Pétillon
authors.forename: Philippe
authors.initials: P
authors.lastname: Schollhammer
authors.forename: Jean
authors.initials: J
authors.lastname: Talarmin
mesh_terms: D001665:Binding Sites; D002384:Catalysis; D018360:Crystallography, X-Ray; D004579:Electron Transport; D005290:Ferric Compounds / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry / Q000378:metabolism*; D007506:Iron-Sulfur Proteins / Q000737:chemistry / Q000378:metabolism*; D008958:Models, Molecular; D019906:Nuclear Magnetic Resonance, Biomolecular; D013055:Spectrophotometry, Infrared; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D007506:Iron-Sulfur Proteins; D013438:Sulfhydryl Compounds; C002007:dithiol-iron(III)-sulfide complex; C118830:iron hydrogenase; D006864:Hydrogenase