title: Electrochemical hydrogen production in aqueous micellar solution by a diiron benzenedithiolate complex relevant to [FeFe] hydrogenases.
abstract: The diiron hydrogenase model Fe(2)(bdt)(CO)(6) (1, bdt = benzenedithiolate) was dispersed in aqueous micellar solution prepared from sodium dodecyl sulfate (SDS). Aqueous solution of 1 showed no sign of decomposition when left in contact with air over a period of several days. Current-potential responses recorded at a dropping mercury electrode over pH 7-3 were consistent with reduction of freely diffusing species. Catalysis of proton reduction was observed at pH < 6 with current densities exceeding 0.5 mA cm(-2) at an acid-to-catalyst ratio of 17. Bulk electrolysis at -0.66 V vs. SHE of solution of 1 at pH 3 confirmed the production of hydrogen with a Faradaic efficiency close to 100%. A mechanism involving initial reduction of 1 and subsequent proton-coupled electron transfer is proposed.
authors.affiliation: UMR 6521, CNRS, Université de Bretagne Occidentale, 6 Av Le Gorgeu, Brest, France.  fgloague@univ-brest.fr.
authors.forename: François
authors.initials: F
authors.lastname: Quentel
authors.forename: Guillaume
authors.initials: G
authors.lastname: Passard
authors.forename: Frederic
authors.initials: F
authors.lastname: Gloaguen