title: Electrocatalytic water oxidation by a monomeric amidate-ligated Fe(III)-aqua complex.
abstract: The six-coordinate Fe(III)-aqua complex [Fe(III)(dpaq)(H2O)](2+) (1, dpaq is 2-[bis(pyridine-2-ylmethyl)]amino-N-quinolin-8-yl-acetamido) is an electrocatalyst for water oxidation in propylene carbonate-water mixtures. An electrochemical kinetics study has revealed that water oxidation occurs by oxidation to Fe(V)(O)(2+) followed by a reaction first order in catalyst and added water, respectively, with ko = 0.035(4) M(-1) s(-1) by the single-site mechanism found previously for Ru and Ir water oxidation catalysts. Sustained water oxidation catalysis occurs at a high surface area electrode to give O2 through at least 29 turnovers over an 15 h electrolysis period with a 45% Faradaic yield and no observable decomposition of the catalyst.
authors.affiliation: Department of Chemistry, University of North Carolina at Chapel Hill , Chapel Hill, North Carolina 27599, United States.
authors.forename: Michael K
authors.initials: MK
authors.lastname: Coggins
authors.forename: Ming-Tian
authors.initials: MT
authors.lastname: Zhang
authors.forename: Aaron K
authors.initials: AK
authors.lastname: Vannucci
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Dares
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Meyer
mesh_terms: D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D004563:Electrochemistry; D005290:Ferric Compounds / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D014867:Water / Q000737:chemistry*
chemical_list: D000577:Amides; D005290:Ferric Compounds; D014867:Water