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Oxidised metallophenolicporphyrins as models for compound I of the peroxidases. Reduction of oxidised iron(III), nickel(II) and zinc(II) complexes of meso-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)prophyrin by the peroxidase substrate p-cresol

DAEID, N N and NOLAN, K B (1993) Oxidised metallophenolicporphyrins as models for compound I of the peroxidases. Reduction of oxidised iron(III), nickel(II) and zinc(II) complexes of meso-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)prophyrin by the peroxidase substrate p-cresol. Inorganica Chimica Acta, 211 (1). pp. 55-60. ISSN 0020-1693

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Abstract

Oxidised metal complexes of meso-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)porphyrin (3), M-TBHPP(ox), react with peroxidase substrates such as p-cresol regenerating the parent metalloporphyrins cleanly and quantitatively. The kinetics of the reduction of the oxidised iron(III), nickel(II) and zinc(II) porphyrin complexes in chloroform and methanol have been investigated. Generally rate expressions of the form, rate={k1+k2[p-cresol]}[M-TBHPP(ox)] were observed where the k1 term represents an auto- or solvent-assisted reduction pathway while the k2 term represents a reduction pathway involving p-cresol. For the reduction of Ni-TBHPP(ox) in chloroform however a rate expression of the form rate={k1+k3[p-cresol]2}[Ni-TBHPP(ox)] was observed, the second order dependence of rate on p-cresol concentration being attributed to pre-equilibrium formation of a p-cresol dimer which in the rate determining step is the active reductant. Rate constants for the above reactions are reported as well as activation parameters for the reduction of the oxidised nickel(II) complex in both solvents.

Item type: Article
ID code: 33469
Keywords: facile aerial oxidation, porphyrin, cytochrome, ligands, metals, Physical and theoretical chemistry, Materials Chemistry, Physical and Theoretical Chemistry, Inorganic Chemistry
Subjects: Science > Chemistry > Physical and theoretical chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Related URLs:
    Depositing user: Pure Administrator
    Date Deposited: 17 Oct 2011 10:50
    Last modified: 05 Sep 2014 10:50
    URI: http://strathprints.strath.ac.uk/id/eprint/33469

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