Süss-Fink, Georg

2007, Kozlov, Yuriy N, Romakh, Vladimir B, Kitaygorodskiy, Alex, Buglyo, Peter, Süss-Fink, Georg, Shul'pin, Georgiy B

The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA equivalent to pcaH) efficiently catalyzes the oxidation of 2-propanol by hydrogen peroxide to give acetone. UV-vis spectroscopic monitoring of the reaction as well as the kinetics lead to the conclusion that the crucial step of the process is the monomolecular decomposition of a diperoxovanadium(V) complex containing the pca ligand to afford the peroxyl radical, HOO center dot and a V(IV) derivative. The rate-limiting step in the overall process may not be this (rapid) decomposition itself but (prior to this step) the slow hydrogen transfer from a coordinated H2O2 molecule to the oxygen atom of a pca ligand at the vanadium center: "(pca)(O)V center dot center dot center dot O2H2" -> "(pca)(HO-)V-OOH". The V(IV) derivative reacts with a new hydrogen peroxide molecule to generate the hydroxyl radical ("V-IV" + H2O2 -> "V-V" + HO- + HO center dot), active in the activation of isopropanol: HO center dot + Me2CH(OH) -> H2O + Me2C center dot(OH). The reaction with an alkane, RH, in acetonitrile proceeds analogously, and in this case the hydroxyl radical abstracts a hydrogen atom from the alkane: HO center dot + RH -> H2O + R-center dot. These conclusions are in a good agreement with the results obtained by Bell and co-workers (Khaliullin, R. Z.; Bell, A. T.; Head-Gordon, M. J. Phys. Chem. B 2005, 109, 17984-17992) who recently carried out a density functional theory study of the mechanism of radical generation in the reagent under discussion in acetonitrile.

2006, Shul'pin, Georgiy B, Sooknoi, Tawan, Romakh, Vladimir B, Süss-Fink, Georg, Shul'pina, Lidia S

Titanosilicalite TS-1 catalyses oxidation of light (methane, ethane, propane and n-butane) and normal higher (hexane, heptane, octane and nonane) alkanes to give the corresponding isomeric alcohols and ketones. The oxidation of higher alkanes proceeds in many cases with a unique regioselectivity. Thus, in the reaction with n-heptane the CH2 groups in position 3 exhibited a reactivity 2.5 times higher than those of the other methylene groups. This selectivity can be enhanced if hexan-3-ol is added to the reaction mixture, the 3-CH2/2-CH2 ratio becoming 10. It is assumed that the unusual selectivity in the oxidation of n-heptane (and other higher alkanes) is due to steric hindrance in the catalyst cavity. As a result, the catalytically active species situated on the catalyst walls can only easily react with certain methylenes of the alkane, which is adsorbed in the cavity taking U-shape (hairpin) conformations. (c) 2006 Elsevier Ltd. All rights reserved.

2005, Shul'pin, Georgiy B, Golfeto, Camilla C, Süss-Fink, Georg, Shul'pina, Lidia S, Mandelli, Dalma

The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60 degrees C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide. (c) 2005 Elsevier Ltd. All rights reserved.