Abstract
Bimolecular reactions of the antimony(V) porphyrin complexes SbO(tpp)OH, 1 and SbO(oep)OH. 2 with tetra-n-butylammonium hydroxide were investigated at 298 K in acetonitrile solution (tpp, dianion of 5,10,15,20-tetraphenylporphyrin and oep, dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin). Spontaneous nucleophilic addition of hydroxide ions to the non-oxidized porphyrin macrocycle leads to novel ...
Abstract
Bimolecular reactions of the antimony(V) porphyrin complexes SbO(tpp)OH, 1 and SbO(oep)OH. 2 with tetra-n-butylammonium hydroxide were investigated at 298 K in acetonitrile solution (tpp, dianion of 5,10,15,20-tetraphenylporphyrin and oep, dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin). Spontaneous nucleophilic addition of hydroxide ions to the non-oxidized porphyrin macrocycle leads to novel hydroxyphlorin derivatives, which contain a saturated meso-carbon bridge. While this process is a reversible equilibrium reaction for the TPP derivative, the OEP complex undergoes subsequent demetallation and oxidative ring cleavage in the presence of dioxygen. Possible implications for the competitive inhibition of heme-oxygenase by high-valent metalloporphyrin therapeutics are discussed. (C) 2001 Elsevier Science B.V. All rights reserved.
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