PREPARATION, CATALYTIC ACTIVITY OF SUPPORTED METALLOPORPHYRIN CATALYSTS ON POLYVINYLPYRIDINE POLYMERS AND RELATED MOLECULAR MODELING STUDIES (CASE OF A PROXIMAL LIGAND PROVIDED BY THE POLYMER ITSELF)

Anionic manganese and iron porphyrin complexes derived from sulfonated TPP, TMP or TDCPP ligands can be easily attached to a poly(4-vinylpyr idinium) polymer. First the metalloporphyrin is linked to the neutral poly(4-vinylpyridine) by a pyridine from the polymer itself, which act s as a proximal ligand. The protonation of the other pyridine residues then reinforces the linkage of metalloporphyrins by additional strong electrostatic interactions (molecular modelling studies confirm this hypothesis). Such supported metallophorphyrins with a proximal ligand arising from the polymer can be used in the potassium monopersulfate o xidation of lignin model molecules in the absence of an excess of free pyridine, which is usually required for efficient manganese porphyrin -catalyzed reactions.