title: Mechanistic implications of the active species involved in the oxidation of hydrocarbons by iron complexes of pyrazine-2-carboxylic acid.
abstract: The reactivity towards H(2)O(2) of the complexes [Fe(pca)(2)(py)(2)].py (1) and Na(2){[Fe(pca(3))](2)O}.2H(2)O.CH(3)CN (2) (where pca(-) is pyrazine-2-carboxylate) and their catalytic activity in the oxidation of hydrocarbons is reported. Addition of H(2)O(2) to 1 results in the formation of a dinuclear Fe(III)-(mu-O)-Fe(III) species characterized spectroscopically and by cyclic voltammetry. By contrast, treatment of 2 with H(2)O(2) results in the formation of mononuclear iron(II) complexes, [Fe(pca)(2)(solvent)(2)]. The experimental results indicate that the catalytic activity of the starting complexes 1 and 2 is strongly dependent on the species formed in solution.
authors.affiliation: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, PO Box 9502, 2300, RA Leiden, The Netherlands.
authors.forename: Stefania
authors.initials: S
authors.lastname: Tanase
authors.forename: Patricia
authors.initials: P
authors.lastname: Marques-Gallego
authors.forename: Wesley R
authors.initials: WR
authors.lastname: Browne
authors.forename: Ronald
authors.initials: R
authors.lastname: Hage
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Bouwman
authors.forename: Ben L
authors.initials: BL
authors.lastname: Feringa
authors.forename: Jan
authors.initials: J
authors.lastname: Reedijk
mesh_terms: D002384:Catalysis; D004563:Electrochemistry; D006838:Hydrocarbons / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011718:Pyrazinamide / Q000031:analogs & derivatives* / Q000737:chemistry; D012996:Solutions / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors
chemical_list: D006838:Hydrocarbons; D009942:Organometallic Compounds; D012996:Solutions; D011718:Pyrazinamide; C005296:pyrazinoic acid; D006861:Hydrogen Peroxide; D007501:Iron