Synthetic porphyrins/metalloporphyrins which mimic states in catalytic cycle of cytochrome P-450 and peroxidases

N. Nic Daeid, S. T. Atkinson, K. B. Nolan (Lead / Corresponding author)

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The reaction of thiolates, RS-, having electron withdrawing groups with iron(III) tetra-arylporphyrins in DMSO,in air gives low-spin Fe(III)-P(-SR)2, having hyperporphyrin spectra similar to thiolate derivatives of cytochrome P-450. Removal of air gives high spin Fe(II)-P(-SR) which on addition of CO results in H+ uptake and formation of Fe(II)-P(SHR)CO. Addition of thiols and base to the iron(III) porphyrins in toluene in the absence of air gives 4-coordinate Fe(II)-P which in the presence of CO gives Fe(II)-P(SHR)CO. Metal complexes of one of the porphyrins studied i.e. a tetraphenolic porphyrin undergo 2e- oxidation in air to give quinonoid species which oxidise peroxidase substrates. Rate constants for some of these reactions are reported.
Original languageEnglish
Pages (from-to)1541-1548
Number of pages8
JournalPure and Applied Chemistry
Volume65
Issue number7
DOIs
Publication statusPublished - 1993
EventInternational Symposium on Macrocyclic Ligands for the Design of New Materials - University of Surrey, Guildford, United Kingdom
Duration: 14 Sep 199216 Sep 1992

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Keywords

  • facile area oxidation, polyvalent porphyrins, complexes, Physical and theoretical chemistry, Chemical Engineering(all), Chemistry(all)

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