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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Metalloporphyrins
Peroxidases
Porphyrins
Carbon Monoxide
Cytochrome P-450 Enzyme System
Air
Iron
Coordination Complexes
Toluene
Metal complexes
Dimethyl Sulfoxide
Sulfhydryl Compounds
Peroxidase
Rate constants
Derivatives
Oxidation
Electrons
Substrates

Keywords

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

Cite this

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title = "Synthetic porphyrins/metalloporphyrins which mimic states in catalytic cycle of cytochrome P-450 and peroxidases",
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.",
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Synthetic porphyrins/metalloporphyrins which mimic states in catalytic cycle of cytochrome P-450 and peroxidases. / Nic Daeid, N.; Atkinson, S. T.; Nolan, K. B. (Lead / Corresponding author).

In: Pure and Applied Chemistry, Vol. 65, No. 7, 1993, p. 1541-1548.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthetic porphyrins/metalloporphyrins which mimic states in catalytic cycle of cytochrome P-450 and peroxidases

AU - Nic Daeid, N.

AU - Atkinson, S. T.

AU - Nolan, K. B.

PY - 1993

Y1 - 1993

N2 - 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.

AB - 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.

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

U2 - 10.1002/chin.199336306

DO - 10.1002/chin.199336306

M3 - Article

VL - 65

SP - 1541

EP - 1548

JO - Pure and Applied Chemistry

JF - Pure and Applied Chemistry

SN - 0033-4545

IS - 7

ER -