I. SYNTHESIS AND PHYSICAL CHARACTERIZATION OF SELECTED POLYSTYRENE SUPPORTED PHTHALOCYANINE COMPLEXES. II. ELECTRON TRANSFER STUDY BETWEEN TITANOCENE DICHLORIDE AND REDUCED TITANOCENE DICHLORIDE ANION

I. For the past four decades the rather weak catalytic activity of phthalocyanine complexes toward oxidation process has been known. As a class, the compounds are inexpensive and widely available due to their use as fabric dyes. The limitation to their catalatic activity was claimed to be caused by dimer formation between phthalocyanine groups.; Recently due to interest in the isoelectric porphyrin system role in biologic oxidation reactions, work has been renewed on the structurally similar phthalocyanines. To be active in oxidation processes these systems rely on site isolation of individual metal ligand complexes. Such a system is reported here.; Nickel, vanadyl, cobalt, iron, and manganese phthalocyanine compounds have been attached to polymers by binding the chlorosulfonated metal phthalocyanines to styrene divinyl benzene (20% and 8% divinyl benzene) copolymers. Attachment by direct sulfonylation and by formation of the sulfonamide linkage were carried out. Physical characterization of the resulting complexes was accomplished by electron spin resonance analysis, transmittance electron microscopy, scanning electron microprobe analysis, and differential scanning calorimetry. The effect of the presence of the polymer resin based complexes in contact with cyclohexene during its oxidation are reported in detail. Additional oxidation reactions with these complexes were attempted with 1- and 2- octene, toulene, and cumene.; II. Biscyclopendadiehyl titanium dichloride (titanocene dichloride) has been reduced with aluminum to give a reduced Ti(III) compound with a pronounced electron spin resonance spectrum. The reduced Ti(III) complex was treated with the parent titanium (IV) complex of titanocene dichloride in tetrahydrofuran. Linewidth broadening of the ESR spectrum allowed calculation of the rate of electron transfer between the Ti(IV) and Ti(III) metal complexes as k = 2.3 x 10('8)M('-1)sec('-1).