Organic Catalysts. IV. The Role of the Iron as an Oxidation Catalyst in Copper-Iron-Polyphthalocyanine

Abstract

The role of the iron in copper-iron-polyphthalocyanine in the catalytic action in the oxidation of acetaldehyde ethylene acetal and cyclohexene was investigated on the basis of the inhibition of the reaction by the treatment of copper-iron-polyphthalocyanine with iron-binding agents and oxidizing agents. The catalytic action of copper-iron-polyphthalocyanine decreased or disappeared upon the addition of 2-phenylimidazole and pyridine to the reaction system, and upon the treatment with bromine or concentrated hydrochloric acid in the presence of air. However, the reduction of the oxidized copper-iron-polyphthalocyanine with ascorbic acid or sodium thiosulfate recovered the catalytic activity. Furthermore, the catalytic activities of iron-metalpolyphthalocyanines (metal; V, Cr, Mn, Co, Ni, Cu and Zn) and copper-metal-polyphthalocyanines (metal; V, Cr, Co, Ni and Zn) in the oxidation of acetaldehyde ethylene acetal were investigated. The former groups showed the catalytic actions, but no catalytic actions were observed in the latter groups. The catalytic activities of iron-metal-polyphthalocyanines increased with a decrease in the activation energy of the electrical conductivity of the polymer. From these results, it was presumed that the Fe(II) ions located in the conjugated system act as active sites for the activation of oxygen and for the decomposition of peroxide.

Catalytic Activity of Binuclear Transition Metal Phthalocyanines in Electrolyte Operation of Lithium/Thionyl Chloride Battery

“…Therefore, the catalysis of binuclear metal phthalocyanines has become a focal point of research work. 16,17 In resent years, our research group has studied the impact of mononuclear transition metal phthalocyanines to Li/SOCl 2 battery. [18][19][20][21][22] It is found that when the transition metal phthalocyanines are added to the electrolyte of the battery, the discharge capability of the battery is improved obviously.…”