1.10- Phenanthroline, reaction with rhodium complexes

Theoretically, in a simple kinetic resolution the ee value should not exceed 32 % at this specific conversion. In addition to the rhodium complex, this reaction requires acetophenone as stoichiometric hydride acceptor, phenanthroline as coligand and potassium hydroxide as base. An ee value of 98 % at 60 % conversion (theoretical value 67 %)is achieved with [Rh2(OAc)4] without an added base after 3 days. Surprisingly, the enzyme tolerates potassium hydroxide in amounts up to 20 mol% at elevated temperatures however, the enantiomeric excesses are somewhat lower than those obtained in an ordinary kinetic resolution. Unselective, base- or metal-catalyzed acylation might be the reason for the somewhat lower ee value. 

The oxidation of HCO2 is induced by the reaction of the Cu(I) complex of phenanthroline with 11202 The reaction has been studied by radiolysis of the Cu(II) complex and by mixing high concentrations of the Cu(I) species with H2O2 and HC02 It is proposed that the peroxo complex, [(phen)2CuH202], oxidized HCO2 with a rate constant of 3 x 10 s" Cationic rhodium complexes... 

With transition metal complexes (typically rhodium compounds), it is possible to functionalize pyrrole and to obtain active electrodes for the hydrogenation of ketones. An example showing the behaviour of a film of poly(pyiTole-Rh(lll)bipyridyl) is the reduction of cyclohexanone into cyclohexanol with a chemical yield of 79% [110], This molecular electrode is also suitable for the reduction of water in hydrogen, Electrocatalytic hydrogenation of other ketones, unsaturated ketones or aldehydes, has been studied recently [174-176], These hydrogenation reactions are performed in an aqueous medium and the modified electrodes are obtained after electropolymerization of pyrrole substituted 2,2 -bipy-ridine or 1,10-phenanthroline complexes of Pd(Il) or of Rh(Ill). More precisely, with the Pd(ll) complex... 

Preliminary results of the reaction between vanadium(iii)-tetrasulpho-phthalocyanine complex with oxygen have been reported these data were compared with those obtained for the corresponding reaction of the hexa-aquo complex ion. The oxidation of methyl ethyl ketone by oxygen in the presence of Mn"-phenanthroline complexes has been studied Mn " complexes were detected as intermediates in the reaction and the enolic form of the ketone hydroperoxide decomposed in a free-radical mechanism. In the oxidation of 1,3,5-trimethylcyclohexane, transition-metal [Cu", Co", Ni", and Fe"] laurates act as catalysts and whereas in the absence of these complexes there is pronounced hydroperoxide formation, this falls to a low stationary concentration in the presence of these species, the assumption being made that a metal-hydroperoxide complex is the initiator in the radical reaction. In the case of nickel, the presence of such hydroperoxides is considered to stabilise the Ni"02 complex. Ruthenium(i) chloride complexes in dimethylacetamide are active hydrogenation catalysts for olefinic substrates but in the presence of oxygen, the metal ion is oxidised to ruthenium(m), the reaction proceeding stoicheiometrically. Rhodium(i) carbonyl halides have also been shown to catalyse the oxidation of carbon monoxide to carbon dioxide under acidic conditions ... 

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