title: Kinetic and mechanistic studies on the reaction of nitric oxide with a water-soluble octa-anionic iron(III) porphyrin complex.
abstract: The polyanionic water-soluble and non-mu-oxo-dimer-forming iron porphyrin iron(III) 5(4),10(4),15(4),20(4)-tetra-tert-butyl-5(2),5(6),15(2),15(6)-tetrakis[2,2-bis(carboxylato)ethyl]-5,10,15,20-tetraphenylporphyrin, (P(8-))Fe(III) (1), was synthesized as an octasodium salt by applying well-established porphyrin and organic chemistry procedures to bromomethylated precursor porphyrins and characterized by standard techniques such as UV-vis and (1)H NMR spectroscopy. A single pK(a1) value of 9.26 was determined for the deprotonation of coordinated water in (P(8-))Fe(III)(H(2)O)(2) (1-H(2)()O) present in aqueous solution at pH <9. The porphyrin complex reversibly binds NO in aqueous solution to give the mononitrosyl adduct, (P(8-))Fe(II)(NO(+))(L), where L = H(2)O or OH(-). The kinetics of the binding and release of NO was studied as a function of pH, temperature, and pressure by stopped-flow and laser flash photolysis techniques. The diaqua-ligated form of the porphyrin complex binds and releases NO according to a dissociative interchange mechanism based on the positive values of the activation parameters DeltaS() and DeltaV() for the "on" and "off" reactions. The rate constant k(on) = 6.2 x 10(4) M(-1) s(-1) (24 degrees C), determined for NO binding to the monohydroxo-ligated (P(8-))Fe(III)(OH) (1-OH) present in solution at pH >9, is markedly lower than the corresponding value measured for 1-H(2)O at lower pH (k(on) = 8.2 x 10(5) M(-1) s(-1), 24 degrees C, pH 7). The observed decrease in the reactivity is contradictory to that expected for the diaqua- and monohydroxo-ligated forms of the iron(III) complex and is accounted for in terms of a mechanistic changeover observed for 1-H(2)O and 1-OH in their reactions with NO. The mechanistic interpretation offered is further substantiated by the results of water-exchange studies performed on the polyanionic porphyrin complex as a function of pH, temperature, and pressure.
authors.affiliation: Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Germany.
authors.forename: Joo-Eun
authors.initials: JE
authors.lastname: Jee
authors.forename: Siegfried
authors.initials: S
authors.lastname: Eigler
authors.forename: Frank
authors.initials: F
authors.lastname: Hampel
authors.forename: Norbert
authors.initials: N
authors.lastname: Jux
authors.forename: Maria
authors.initials: M
authors.lastname: Wolak
authors.forename: Achim
authors.initials: A
authors.lastname: Zahl
authors.forename: Grazyna
authors.initials: G
authors.lastname: Stochel
authors.forename: Rudi
authors.initials: R
authors.lastname: van Eldik
mesh_terms: D000838:Anions / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D008665:Metalloporphyrins / Q000737:chemistry* / Q000378:metabolism; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry* / Q000378:metabolism; D012995:Solubility; D014867:Water / Q000737:chemistry*
chemical_list: D000838:Anions; D008665:Metalloporphyrins; D014867:Water; D009569:Nitric Oxide; D007501:Iron