Synthetic Porphyrins/Metalloporphyrins Which Mimic States in Catalytic Cycle of Cytochrome P-450 and Peroxidases

N N DAEID, S T ATKINSON, K B NOLAN

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.

LanguageEnglish
Pages1541-1548
Number of pages8
JournalPure and Applied Chemistry
Volume65
Issue number7
DOIs
Publication statusPublished - Jul 1993

Fingerprint

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
tebufenozide
Electrons
Substrates

Keywords

  • facile area oxidation
  • polyvalent porphyrins
  • complexes

Cite this

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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. / DAEID, N N ; ATKINSON, S T ; NOLAN, K B .

In: Pure and Applied Chemistry, Vol. 65, No. 7, 07.1993, 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 - DAEID, N N

AU - ATKINSON, S T

AU - NOLAN, K B

PY - 1993/7

Y1 - 1993/7

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

KW - polyvalent porphyrins

KW - complexes

U2 - 10.1002/chin.199336306

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JO - Pure and Applied Chemistry

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SN - 0033-4545

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