Redox reactions of osmium porphyrins
- 1 January 1988
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 11,p. 2705-2711
- https://doi.org/10.1039/dt9880002705
Abstract
The metal centre in osmium porphyrinates (OsP) can exist in a wide range of oxidation states, each being stabilised by axial complexation with a particular ligand. Thus, OsIIP is stabilised by ligation with a CO molecule. Oxidation occurs readily to form the corresponding OsIIIP which retains the CO ligand and can be reduced quantitatively to the original OsII complex. Further oxidation gives OsIVP which is stabilised by axial ligation of two alcohol or water molecules. These OsIV complexes are stable to both oxidation and reduction. Treating the OsIIP with an organic peroxide results in formation of an OsVIP complex which is stabilised by two oxo ligands but can be reduced to the OsIVP species. Photolysis of OsIIP and OsIIIP causes loss of the CO ligand, the naked porphyrin species so formed undergoes oxidative reactions with the solvent, O2, or trace impurities, in most cases forming an OsIVP complex. The [OsVIP(O)2] species does not oxidise alkanes or alkenes in the dark at room temperature but does oxidise cyclohexene under visible light irradiation.Keywords
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