Manganese complexes thiols

Phthalocyanlnes. Gebler (18) has reported the attachment of a variety of metal phthalocyanines to both 8% and 20% dlvlnylbenzene polystyrene copolymer beads. The attachment of the phthalocyanine unit was either ly a sulfonamide or a sulfone linkage. Nickel, vanadyl, cobalt, iron and manganese complexes were formed in this way. Since solution aggregation accounts for a diminution of the catalytic activity, it was anticipated that polymer immobilization would Increase reactivity. Such an effect was not observed and little advantage over the homogeneous catalysts could be observed in the oxidation of cyclohexene. Oxidations of thiols by immobilized phthalocyanines have been reported (19-20) by both Schutten and Brouwer. 

More traditional O2 oxidation experiments were attempted with the vaulted iron and manganese complexes in several solvents with many of the reducing agents (ascorbic acid, sodium ascorbate, thiols, borohydride, and amalgamated zinc) that have been used elsewhere in work with porphyrins and their derivatives. " The more promising systems are mentioned here. Various thiols, such as thioglycol ethyl ester and P-mercaptoethanol, were... 

Cr QRt ]2, to various types of bridges, one example being the manganese(III) complex (12-XXXI). Thiols such as HSCH2C02Et can give more complicated species such as Nig(SCH2C02Et)16. 

Early work on the catalytic autoxidation of carboxythiols confirmed the effectiveness of manganese, iron, cobalt, copper, and arsenic, but the first major assault on the mechanism of the reaction was due to Michaelis and Barron [123,124]. The oxidation of cysteine at pH 7—8 was found to be zero order in cysteine and to involve metal—cysteine complexes as active intermediates. Several studies of metal—thiol complexes have been... 

---