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.
|Number of pages||8|
|Journal||Pure and Applied Chemistry|
|Publication status||Published - 1993|
|Event||International Symposium on Macrocyclic Ligands for the Design of New Materials - University of Surrey, Guildford, United Kingdom|
Duration: 14 Sep 1992 → 16 Sep 1992
- facile area oxidation, polyvalent porphyrins, complexes, Physical and theoretical chemistry, Chemical Engineering(all), Chemistry(all)
Nic Daeid, N., Atkinson, S. T., & Nolan, K. B. (1993). Synthetic porphyrins/metalloporphyrins which mimic states in catalytic cycle of cytochrome P-450 and peroxidases. Pure and Applied Chemistry, 65(7), 1541-1548. https://doi.org/10.1002/chin.199336306