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

N. Nic Daeid; S. T. Atkinson; K. B. Nolan

doi:10.1002/chin.199336306

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)

Leverhulme Research Centre for Forensic Science

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	1541-1548
Number of pages	8
Journal	Pure and Applied Chemistry
Volume	65
Issue number	7
DOIs	https://doi.org/10.1002/chin.199336306
Publication status	Published - 1993
Event	International Symposium on Macrocyclic Ligands for the Design of New Materials - University of Surrey, Guildford, United Kingdom Duration: 14 Sept 1992 → 16 Sept 1992

Keywords

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

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10.1002/chin.199336306

http://www.iupac.org/publications/pac/65/7/

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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.",

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

author = "\{Nic Daeid\}, N. and Atkinson, \{S. T.\} and Nolan, \{K. B.\}",

year = "1993",

doi = "10.1002/chin.199336306",

language = "English",

volume = "65",

pages = "1541--1548",

journal = "Pure and Applied Chemistry",

issn = "0033-4545",

publisher = "Walter de Gruyter GmbH",

number = "7",

note = "International Symposium on Macrocyclic Ligands for the Design of New Materials ; Conference date: 14-09-1992 Through 16-09-1992",

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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

SN - 0033-4545

VL - 65

SP - 1541

EP - 1548

JO - Pure and Applied Chemistry

JF - Pure and Applied Chemistry

IS - 7

T2 - International Symposium on Macrocyclic Ligands for the Design of New Materials

Y2 - 14 September 1992 through 16 September 1992

ER -

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

Abstract

Keywords

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