Phthalocyanine cobalt, reduction

Selective reduction of the aromatic nitro aldehyde 220 to the amine group by phthalocyanine cobalt (I) anion is followed by condensation to alkaloids 221 (Scheme 48) (81AGE208). 

Martins Alves, M.C., J.P. Dodelet, D. Guay, M. Ladouceur, and G. Tourillon (1992). Origin of the electrocatalytic properties for O2 reduction of some heat-treated polyacrylonitrile and phthalocyanine cobalt compounds adsorbed on carbon black as probed by electrochemistry and X-ray absorption spectroscopy. J. Phys. Chem. 96, 10898-10905. 

Zhao, R, J. Zhang, T. Abe, D. Wohrle, and M. Kaneko (1999). Electrocatalytic proton reduction by phthalocyanine cobalt derivatives incorporated in poly(4-vinylpyridine-co-styrene) film. J. Mol. Cat. A Chem. 145, 245-256. 

Lalande G, Cote R, Tamizhmani G, Guay D, Dodelet JP. 1995. Physical, chemical and electrochemical characterization of heat-treated tetracarboxylic cobalt phthalocyanine adsorbed on carbon black as electrocatalyst for oxygen reduction in polymer electrolyte fuel cells. Electrochim Acta 40 2635-2646. 

The first catalysts reported for the electroreduction of C02 were metallophthalocyanines (M-Pc).126 In aqueous solutions of tetraalkylammonium salts, current-potential curves at a cobalt phthalocyanine (Co-Pc)-coated graphite electrode showed a reduction current peak whose height was proportional to the C02 concentration and to the square root of the potential sweep rate at a given C02 concentration. On electrolysis, oxalic acid and glycolic acid were detected, but formic acid was not. Mn and Pd phthalocyanines were inactive, while Cu and Fe phthalocyanines were slightly active. At the potentials used for C02 reduction, M-Pc catalysts would be in their dinegative state, and the occupied dz2 orbital of the metal ion in the metallophthalocyanine was suggested to play an important role in the catalytic activity. 

In contrast to Co-porphyrin complexes, the direct four-electron reduction of 02 has been only very rarely claimed to be catalyzed by a cobalt phthalocyanine 404 407 In particular cofadal binuclear Co-Pc complexes immobilized on pyrolytic graphite catalyze only the two-electron electroreduction of 02 to H202.408,409 However, recent work has established that an electropolymerized Co-Pc derivative provides a stable four-electron reduction pathway over a wide pH range 410... 

The study just described is in accordance with the observation that electrochemical reduction of the (highly conjugated) phthalocyanine (5) complex of Mn(n) also gives no evidence for the formation of a Mn(i) species (in contrast to the corresponding iron and cobalt complexes which, on reduction, yield Fe(i) and Co(i) products) (Lever, Minor Wilshire, 1981). 

Cobalt(I) salen has been employed as a catalyst for the reduction of the following species benzal chloride [159] benzotrichloride [160] 1-bromobutane, 1-iodobutane, and 1,2-dibromobutane [161] iodoethane [162], benzyl chloride [163], and ethyl chloroacetate [164]. Rusling and coworkers have investigated the use of cobalt(I) salen, as well as vitamin Bi2s and cobalt(I) phthalocyanine, in both homogeneous phase and bicontin-uous microemulsions for the catalytic reduction of vicinal dibromides [165] and... 

Transition metal compounds, such as organic macrocycles, are known to be good electrocatalysts for oxygen reduction. Furthermore, they are inactive for alcohol oxidation. Different phthalocyanines and porphyrins of iron and cobalt were thus dispersed in an electron-conducting polymer (polyaniline, polypyrrole) acting as a conducting matrix, either in the form of a tetrasulfonated counter anion or linked to... 

The first chelate found to be electrocatalytic was cobalt phthalocyanine x>, which functions as an oxygen catalyst in alkaline electrolytes. Soon afterwards we were able to show 3,4,10,11) -that several phthalocyanines are also active in commercially important, sulfuric acid containing media. A comparison of various central atoms showed that activity increased in the order Cu Ni iron phthalocyanine, the nature of the carbon substrate plays a very important part FePc is more active on a carbon substrate with basic surface groups than on one with acid surface groups3). This property is however specific to phthalocyanines (Pc). 

TiOz coated with potassium ferrocyanide proved to be an effective catalyst for the reduction of C02 to formic acid and formaldehyde.169 A very stable and reproducible catalytic system was prepared by immobilizing Ni2+ and Ru2+ complexes into Nation membrane, which was used for the selective reduction of C02 to formic acid.170 Formic acid was again formed when Zn and Co phthalocyanines were adsorbed onto a Nation membrane on irradiation with visible light in acidic aqueous solution containing triethanolamine as a hole scavenger. Cobalt comns (B i2) acting as homogeneous catalysts in acetonitrile-methanol solutions induced the formation of formic acid and CO.172... 

Castellani, A. M. Goncalves, J. E. Gushikem, Y. The use of carbon paste electrodes modified with cobalt tetrasulfonated phthalocyanine adsorbed in silica/titania for the reduction of oxygen. Journal of New Materials for Electrochemical Systems (2002) 5(3) 169-172. 

In the presence of anhydrous Cr(II) halide salts, organic halides undergo one-electron reduction to form radical species, which in the presence of a second equivalent of Cr(II) undergo a second one-electron reduction to form organochromium(III) species (Scheme 5)331. This process works well for allyl, vinyl and acetylenic halides, but not for simple alkyl cases. Alkylchromium(III) species can be formed readily, however, in the presence of catalytic amounts of vitamin B12 or cobalt phthalocyanine (CoPc)332. 

Cleavage of fl-halourethanes. Eckert and Ugi have found that urethanes of this type can be cleaved to the amine by treatment with the anion of 1 in acetone or methanol at room temperature. The reaction involves alkylation followed by reductive fragmentation (equation I). The rate of cleavage depends on the structure of the blocking group 2,2,2-trichloroethoxycarbonyl derivatives (R = R = C1) are cleaved within 1-5 minutes. Cobalt(II) phthalocyanine (1) is recovered in almost quantitative yield in reusable form. 

Some papers have appeared that deal with the use of electrodes whose surfaces are modified with materials suitable for the catalytic reduction of halogenated organic compounds. Kerr and coworkers [408] employed a platinum electrode coated with poly-/7-nitrostyrene for the catalytic reduction of l,2-dibromo-l,2-diphenylethane. Catalytic reduction of 1,2-dibromo-l,2-diphenylethane, 1,2-dibromophenylethane, and 1,2-dibromopropane has been achieved with an electrode coated with covalently immobilized cobalt(II) or copper(II) tetraphenylporphyrin [409]. Carbon electrodes modified with /nc50-tetra(/7-aminophenyl)porphyrinatoiron(III) can be used for the catalytic reduction of benzyl bromide, triphenylmethyl bromide, and hexachloroethane when the surface-bound porphyrin is in the Fe(T) state [410]. Metal phthalocyanine-containing films on pyrolytic graphite have been utilized for the catalytic reduction of P anj -1,2-dibromocyclohexane and trichloroacetic acid [411], and copper and nickel phthalocyanines adsorbed onto carbon promote the catalytic reduction of 1,2-dibromobutane, n-<7/ 5-l,2-dibromocyclohexane, and trichloroacetic acid in bicontinuous microemulsions [412]. When carbon electrodes coated with anodically polymerized films of nickel(Il) salen are cathodically polarized to generate nickel(I) sites, it is possible to carry out the catalytic reduction of iodoethane and 2-iodopropane [29] and the reductive intramolecular cyclizations of 1,3-dibromopropane and of 1,4-dibromo- and 1,4-diiodobutane [413]. A volume edited by Murray [414] contains a valuable set of review chapters by experts in the field of chemically modified electrodes. 

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