title: A diferrous dithiolate as a model of the elusive H(ox)(inact) state of the [FeFe] hydrogenases: an electrochemical and theoretical dissection of its redox chemistry.
abstract: The reduction of the Fe(II)Fe(II) complex [Fe2(CO)2{P(OMe)3}2(κ(2)-IMe-CH2-IMe)(μ-CO)(μ-pdt)](2+) (2P(2+); pdt = S(CH2)3S), which is a synthetic model of the H cluster of the [FeFe] hydrogenases in its inactive state, has been investigated electrochemically and theoretically (by density functional theory, DFT) in order to determine the mechanisms, intermediates, and products of the related processes. The electrochemical reduction of 2P(2+) occurs according to an ECE-type reaction where the intervening chemical step is the loss of one P(OMe)3 ligand. This outcome, which is based on cyclic voltammetric experiments, is strongly supported by DFT calculations that provide additional information on the intermediates and the energetics of the reactions involved. The electrochemical reoxidation of the neutral product of the reduction follows an EEC process where the chemical step is the binding of P(OMe)3 to a dicationic intermediate. DFT calculations reveal that this intermediate has an unusual geometry wherein one of the two C-H bonds of a side methylene from the pdt group forms an agostic interaction with one Fe center. This interaction is crucial to stabilize the 32e(-) diferrous center and concomitantly to preserve Fe(II) from binding of weakly coordinating species. Nonetheless, it could be displaced by a relatively stronger electron donor such as H2, which could be relevant for the design of new oxidation catalysts.
authors.affiliation: UMR CNRS 6521 Chimie, Electrochimie Moléculaires et Chimie Analytique, Université de Bretagne Occidentale, UFR Sciences et Techniques , CS 93837, 29238 Brest-Cedex 3, France.
authors.forename: Dounia
authors.initials: D
authors.lastname: Chouffai
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Capon
authors.forename: Luca
authors.initials: L
authors.lastname: De Gioia
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
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Zampella
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D055664:Electrochemical Techniques; D004583:Electrons; D005296:Ferrous Compounds / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry; D007700:Kinetics; D008024:Ligands; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D005296:Ferrous Compounds; D008024:Ligands; D013438:Sulfhydryl Compounds; D006864:Hydrogenase