Biomimetic degradation of lignin and lignin model compounds by synthetic anionic and cationic water soluble manganese and iron porphyrins

The biomimetic oxidation of 5-5' condensed and diphenylmethane lignin model compounds with several water soluble anionic and cationic iron and manganese porphyrins in the presence of hydrogen peroxide is reported. The oxidative efficiency of manganese and iron meso-tetra(2,6-dichloro-3-sulphonatophenyl) porphyrin chloride (TDCSPPMnCl and TDCSPPFeCl, respectively), meso-tetra-3-sulphonatophenyl porphyrin chloride (TSPPMnCl) and manganese meso-tetra(N-methylpyridinio)porphyrin pentaacetate (TPyMePMn(CH3COO)(5)) was compared on the basis of the oxidation extent of the models tested. Manganese porphyrins were found more effective in degrading lignin substructures than iron ones. Among them the cationic TPyMePMn (CH3COO)(5), never used before in lignin oxidation, showed to be the best catalyst. The catalytic activity of porphyrins in hydrogen peroxide oxidation of residual kraft lignin was also investigated. The use of quantitative P-31 NMR allowed the focusing on the occurrence of different degradative pathways depending on the catalyst used. TPyMePMn(CH3COO)(5) was able to perform the most extensive degradation of the lignin structure, as demonstrated by the decrease of aliphatic hydroxyl groups and carboxylic acids. Noteworthy, no significant condensation reactions occurred during manganese porphyrins catalyzed oxidations of residual kraft lignin, while in the presence of iron porphyrins a substantial increase of condensed substructures was detected. (C) 1999 Elsevier Science Ltd. All rights reserved.