Salene complexes, electrooxidation

Extensive work has been carried out on microsensors built from electropolymerized nickel porphyrin films.328,329 Films of Prussian blue (Fe4[Fe(CN)6]3) 345 metal-salen complexes (M = Co, Fe, Cu, Mn)346 or the ferrocene-containing Nin-tetraaza[14] annulene (24),347 also exhibit interesting activity for NO electrooxidation and sensing. 

Electroreduction and electrooxidation of salene (7V,N -bis(salicylidene)-ethyledi-amine) complexes of cobalt and copper studied by Kapturkiewicz and Behr [147] in eight aprotic solvents obey these conditions. These authors were the first to demonstrate experimentally the significant influence of the dielectric relaxation time of solvents on the electrode kinetics. They found earlier [171] that the mechanism of electrode reactions of salene complexes is independent of the solvents applied. No correlation with the prediction of the Marcus theory was found, but the kinetic data correlated well with the viscosity of the solvents and their dielectric relaxation time. However, because the ohmic drop was not well compensated, their rate constants are likely to be too low, as was shown in DMSO by Lasia and coworkers [172]. 

Cp—Cp coupling occurs, probably via the first-formed palladium phenolate (315) to give the bisquinone methide (316), and the latter spontaneously undergoes intramolecular Diels-Alder reaction to the natural lignan carpanone (317) in 46% yield, with stereocontrol at five chiral centers. High yields, up to 94%, have been recorded using oxygen as oxidant with a metal(II)-salen complex as catalyst, e.g. cobalt(II) salen. A low yield of carpanone was also obtained in electrooxidation. 8... 

Indirect electrochemical oxidative carbonylation with a palladium catalyst converts alkynes, carbon monoxide and methanol to substituted dimethyl maleate esters (81). Indirect electrochemical oxidation of dienes can be accomplished with the palladium-hydroquinone system (82). Olefins, ketones and alkylaromatics have been oxidized electrochemically using a Ru(IV) oxidant (83, 84). Indirect electrooxidation of alkylbenzenes can be carried out with cobalt, iron, cerium or manganese ions as the mediator (85). Metalloporphyrins and metal salen complexes have been used as mediators for the oxidation of alkanes and alkenes by oxygen (86-90). Reduction of oxygen and the metalloporphyrin generates an oxoporphyrin that converts an alkene into an epoxide. 

Finally, innovative bimetallic complexes as dissymmetric ligands can easily be built, giving birth to an unprecedented class of metal Schiff base salen complexes that can be successfully electropolymerized concomitantly with an overoxidation process. The electrooxidation of 8-(3-acetylimino-6-methyl-2,... 

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