title: Towards alternatives to anodic water oxidation: basket-handle thiolate Fe(III) porphyrins for electrocatalytic hydrocarbon oxidation.
abstract: Selective electrocatalytic oxidation of hydrocarbons to alcohols, epoxides or other (higher value) oxygenates should in principal present a useful complementary anodic half-cell reaction to cathodic generation of fuels from water or CO(2)  viz. an alternative to oxygen evolution. A series of new basket-handle thiolate Fe(III)  porphyrins have been synthesised and shown to mediate anodic oxidation of hydrocarbons, specifically adamantane hydroxylation and cyclooctene epoxidation. We compare yields obtained by electrochemical and chemical oxidation of the thiolate porphyrins and benchmark their behaviour against that of Fe(III)  tetraphenyl porphyrin chloride and its tetrapentafluorophenyl analogue.
authors.affiliation: Energy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ, United Kingdom.
authors.forename: Peiyi
authors.initials: P
authors.lastname: Li
authors.forename: Khalaf
authors.initials: K
authors.lastname: Alenezi
authors.forename: Saad K
authors.initials: SK
authors.lastname: Ibrahim
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Wright
authors.forename: David L
authors.initials: DL
authors.lastname: Hughes
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Pickett
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D004566:Electrodes; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014867:Water / Q000737:chemistry*; D005464:Fluorobenzenes; D005466:Fluorocarbons
chemical_list: D005290:Ferric Compounds; D008665:Metalloporphyrins; D013457:Sulfur Compounds; D014867:Water; C093411:tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride; D005464:Fluorobenzenes; D005466:Fluorocarbons