Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C.

The open circuit potential (OCP) established by the quasi-equilibrated electrode reaction of H and HO, complicates catalytic reactions significantly. The hydrogenolysis rate of benzylic alcohol on Pd/C increases 2-3 orders of magnitude with the pH decreasing from 7 to 0.6.

Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis.

Active sites in carbon-catalyzed phosgene synthesis from gaseous CO and Cl2 have been identified using C60 fullerene as a model catalyst. The carbon atoms distorted from sp(2) coordination in non-planar carbon units are concluded to generate active Cl2 . Experiments and density functional theory calculations indicate the formation of a surface-bound [C60 ⋅⋅⋅Cl2 ] chlorine species with radical character as key intermediate during phosgene formation.

Kinetics and mechanism of the [Ru(III)(edta)(H2O)](-)-mediated oxidation of cysteine by H2O2.

The kinetics and mechanism of the [Ru(III)(edta)(H(2)O)](-)-mediated oxidation of cysteine (RSH) by hydrogen peroxide (edta(4-) = ethylenediaminetetraacetate), were studied in detail as a function of both the hydrogen peroxide and cysteine concentrations at pH 5.1 and room temperature. The kinetic traces reveal clear evidence for a catalytic process in which hydrogen peroxide reacts directly with cysteine coordinated to the Ru(III)(edta) complex in the form of [Ru(III)(edta)SR](2-).

Remarkably high catalytic activity of the Ru(III)(edta)/H2O2 system towards degradation of the azo-dye Orange II.

The Ru(III)(edta)/H(2)O(2) system (edta(4-) = ethylenediaminetretaacetate) was found to degrade the azo-dye Orange II at remarkably high efficiency under ambient conditions. Catalytic degradation of the dye was studied by using rapid-scan spectrophotometry as a function of [H(2)O(2)], [Orange II] and pH. Spectral analyses and kinetic data point towards a catalytic pathway involving the rapid formation of [Ru(III)(edta)(OOH)](2-) followed by the immediate subsequent degradation of Orange II prior to the conversion of [Ru(III)(edta)(OOH)](2-) to [Ru(IV)(edta)(OH)](-) and [Ru(V)(edta)(O)](-)via homolysis and heterolysis of the O-O bond, respectively.

Comparative study of the catalytic activity of [Mn(II)(bpy)2Cl2] and [Mn2(III/IV)(mu-O)2(bpy)4](ClO4)3 in the H2O2 induced oxidation of organic dyes in carbonate buffered aqueous solution.

The kinetics of the hydrogen peroxide induced oxidative degradation of the azo dye Orange II in aqueous carbonate buffered solution were studied for the oxo-bridged [Mn(2)(III/IV)(mu-O)(2)(bpy)(4)](ClO(4))(3) complex and its mononuclear analogue [Mn(II)(bpy)(2)Cl(2)] as catalysts to reveal the underlying reaction mechanism and reactive intermediates participating in the catalytic cycle. Both catalysts show identical oxidative reactivity when used at equimolar manganese concentration. If a simple Mn(II) salt and a 1 : 2 concentration of bipyridine are added to the substrate and oxidant containing reaction mixture, the same oxidative reactivity as found for both readily prepared catalysts was observed for several investigated substrates.

[Ru(III)(edta)(H(2)O)](-) mediated oxidation of hydroxyurea with H(2)O(2). Kinetic and mechanistic investigation.

Reported in this paper is the first example of a ruthenium complex, [Ru(III)(edta)(H(2)O)](-) (edta = ethylenediaminetetra-acetate), that catalyzes the oxidation of hydroxyurea in the presence of H(2)O(2), mimicking the action of peroxidase or catalase and shedding light on their possible mechanism of action.

Mechanistic information from volume profiles for water exchange and complex-formation reactions of aquated Ni(II). pH, buffer and medium effects.

Rate and activation parameters for the complex-formation reaction of Ni(2+) with 4-(2-pyridylazo)-N,N-dimethyl aniline (PADA) were studied as a function of pH in different buffers in both aqueous and sodium dodecyl sulfate (SDS) micelle solutions. In aqueous Tris buffer solution, the forward and backward rate constants increased with increasing pH, while the complex-formation constant decreased due to a larger increase in the backward rate constant. The activation entropy, DeltaS(#), and activation volume, DeltaV(#), changed with increasing pH from positive to negative values, suggesting an apparent changeover from a dissociative to a more associative mechanism.

Experimental and theoretical investigations on the catalytic hydrosilylation of carbon dioxide with ruthenium nitrile complexes.

Ruthenium complexes, mer-[RuX(3)(MeCN)(3)] and cis/trans-[RuX(2)(MeCN)(4)] with X=Br, Cl, were investigated as precatalysts in homogeneously catalyzed hydrosilylation of CO(2). The oxidation state of ruthenium and nature of the halide in the precatalysts were found to influence the catalytic activity in the conversion of Me(2)PhSiH to the formoxysilane Me(2)PhSiOCHO, with Ru(III) having chloride ligands being most active. Monitoring the reactions by in-situ IR spectroscopy in MeCN as the solvent indicates an interaction of the precatalyst with the silane prior to activation of CO(2).