Oxidative polymerization of 2,6-dimethylphenol with semiconducting organic polymeric metal complexes containing the bis(ethylene-1,2-dithiolato)copper (II) structure, 1

In the oxidative polymerization of 2,6-dimethylphenol ( 8 ) the catalytic activities of the following semiconducting organic polymeric metal complexes were studied: polymeric complexes containing bis(ethylene-1,2-dithiolato)Cu(II) or Fe(III) complexes and copper(II) phthalocyanine structures ( 3a – c ), catalysts consisting of bis(ethylene-1,2-dithiolato)-Cu(II) or Fe(III) complex structures and hemiporphyrazine type structures ( 5a – c ), and also polymers containing a copper complex of dimercaptomaleic acid monoamide ( 7 ). It was found that a suspension of the insoluble bis(ethylene-1,2-dithiolato)Cu(II) polymeric complexes of type 3 catalyzes the polymerization in the presence of oxygen in pyridine at room temperature producing poly[oxy-(2,6-dimethyl-1,4-phenylene)] ( 9 ) in very good yields. Polymeric complexes of type 5 were inactive by themselves. However, we showed that bis(ethylene-1,2-dithiolato)Cu(II) polymeric complexes of both the 3 and 5 type possess great activities if they are used in the presence of small amounts of copper(II)-pyridine complex in pyridine solution (the chosen concentration was so low that the Cu(II)-pyridine complex alone had only a small activity). Bis(ethylene-1,2-dithiolato)Fe(III) complexes of both the 3 and 5 type were inactive even in the presence of the Cu(II)-pyridine complex.