title: Non-innocent bma ligand in a dissymetrically disubstituted diiron dithiolate related to the active site of the [FeFe] hydrogenases.
abstract: The purpose of the present study was to evaluate the use of a non-innocent ligand as a surrogate of the anchored [4Fe4S] cubane in a synthetic mimic of the [FeFe] hydrogenase active site. Reaction of 2,3-bis(diphenylphosphino) maleic anhydride (bma) with [Fe(2)(CO)(6)(mu-pdt)] (propanedithiolate, pdt=S(CH(2))(3)S) in the presence of Me(3)NO-2H(2)O afforded the monosubstituted derivative [Fe(2)(CO)(5)(Me(2)NCH(2)PPh(2))(mu-pdt)] (1). This results from the decomposition of the bma ligand and the apparent C-H bond cleavage in the released trimethylamine. Reaction under photolytic conditions afforded [Fe(2)(CO)(4)(bma)(mu-pdt)] (2). Compounds 1 and 2 were characterized by IR, NMR and X-ray diffraction. Voltammetric study indicated that the primary reduction of 2 is centered on the bma ligand.
authors.affiliation: Université Européenne de Bretagne, Université de Bretagne Occidentale, CNRS, UMR 6521, Chimie, Electrochimie Moléculaires et Chimie Analytique, ISSTB, CS 93837, Brest, France.
authors.forename: Youtao
authors.initials: Y
authors.lastname: Si
authors.forename: Kévin
authors.initials: K
authors.lastname: Charreteur
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Capon
authors.forename: Frederic
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: D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry; D020134:Catalytic Domain; D055664:Electrochemical Techniques; D005290:Ferric Compounds / Q000737:chemistry*; D006864:Hydrogenase / Q000138:chemical synthesis / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008299:Maleic Anhydrides / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D010782:Photolysis; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D005290:Ferric Compounds; D007506:Iron-Sulfur Proteins; D008299:Maleic Anhydrides; D010720:Phosphines; D013438:Sulfhydryl Compounds; C002007:dithiol-iron(III)-sulfide complex; C118830:iron hydrogenase; D006864:Hydrogenase