Boris N. Shelimov

Photoinduced reactions of methane with molybdena supported on silica

Photoinduced reactions of methane on the surface of molybdena–silica have been studied using u.v. irradiation in the temperature range 293–773 K. During irradiation, photoadsorption of methane (up to 300 mmol of CH4 per mol of Mo) is found to be the predominant process with barely detectable formation of gaseous products. During heating of the irradiated samples from 293 to 473 K, in addition to thermodesorption of methane, which reaches 40–50% of photoadsorbed CH4, the desorption of considerable amounts of ethylene, ethane, hydrogen and smaller amounts of C3 and C4 alkenes and alkanes is observed. E.s.r., u.v.–visible and i.r. measurements of the irradiated samples show the presence of Mo5+ and M4+ ions as well as complexes of Mo4+ with olefins. The effects of O2, N2O and H2O on the photoinduced reactions of methane and on thermodesorption of the products have also been studied. Possible reaction mechanisms for the photoadsorption of methane and for the formation of C2 and higher hydrocarbons are discussed.

Photocatalytic removal of nitrogen oxides from air on TiO2 modified with bases and platinum

The efficiency of TiO2 (Degussa P-25) modified with an alkaline admixture (urea, BaO), sulfuric acid, or platinum in the photocatalytic oxidation of NO (50 ppm) with a flowing 7% O2 + N2 mixture under UV irradiation in a flow reactor at room temperature and atmospheric pressure is reported. Because of the progressive blocking of active sites of the photocatalyst by the reaction products (NO2, NO3−), it is impossible to realize prolonged continuous removal of NOx (NO + NO2) from air without catalyst regeneration at elevated temperatures. The efficiency of the photocatalysts is characterized by specific photoadsorption capacity (SPC) calculated from the total amount of NOx adsorbed during 2-h-long irradiation. Modification of TiO2 with 5% BaO or 5% urea raises the SPC of the catalyst by a factor of 2–3. Presumably, this promoting effect is due to the basic properties of these dopants, which readily sorb NO2 and NO3−. A considerable favorable effect on SPC is also attained by adding 0.5% Pt to (5% BaO)/TiO2. The SPC of the (0.5% Pt)/TiO2 catalyst depends on the state of the platinum. The samples calcined in air at 500°C, which contain Pt+ and Pt2+, have an approximately 2 times higher SPC than unpromoted TiO2 and ensure a much larger NO2/NO ratio at the reactor outlet. Conversely, the samples reduced in an H2 atmosphere at 200°C, whose platinum is in the Pt0 state, show a lower SPC than the initial TiO2 and cause no significant change in the NO2/NO ratio.

Well-Known Mediators of Selective Oxidation with Unknown Electronic Structure: Metal-Free Generation and EPR Study of Imide-N-oxyl Radicals.

Nitroxyl radicals are widely used in chemistry, materials sciences, and biology. Imide-N-oxyl radicals are subclass of unique nitroxyl radicals that proved to be useful catalysts and mediators of selective oxidation and CH-functionalization. An efficient metal-free method was developed for the generation of imide-N-oxyl radicals from N-hydroxyimides at room temperature by the reaction with (diacetoxyiodo)benzene. The method allows for the production of high concentrations of free radicals and provides high resolution of their EPR spectra exhibiting the superhyperfine structure from benzene ring protons distant from the radical center. An analysis of the spectra shows that, regardless of the electronic effects of the substituents in the benzene ring, the superhyperfine coupling constant of an unpaired electron with the distant protons at positions 4 and 5 of the aromatic system is substantially greater than that with the protons at positions 3 and 6 that are closer to the N-oxyl radical center. This is indicative of an unusual character of the spin density distribution of the unpaired electron in substituted phthalimide-N-oxyl radicals. Understanding of the nature of the electron density distribution in imide-N-oxyl radicals may be useful for the development of commercial mediators of oxidation based on N-hydroxyimides.

Selective cross-dehydrogenative C–O coupling of N-hydroxy compounds with pyrazolones. Introduction of the diacetyliminoxyl radical into the practice of organic synthesis

Oxidative C–O coupling of pyrazolones with N-hydroxy compounds of different classes (N-hydroxyphthalimide, N-hydroxybenzotriazole, oximes) was achieved; both one-electron oxidants (Fe(ClO4)3, (NH4)2Ce(NO3)6) and two-electron oxidants (PhI(OAc)2, Pb(OAc)4) are applicable, and the yields reach 91%. Apparently, the coupling proceeds via the formation of N-oxyl radicals from N-hydroxy compounds. One of the N-oxyl intermediates, the diacetyliminoxyl radical, was found to be exclusively stable in solution in spite of being sterically unhindered; it was isolated from an oxidant and used as a new reagent for the synthesis and mechanism study. The products of C–O coupling of pyrazolones with N-hydroxyphthalimide can be easily transformed into aminooxy compounds, valuable substances for combinatorial chemistry.

Iminoxyl radicals vs. tert-butylperoxyl radical in competitive oxidative C–O coupling with β-dicarbonyl compounds. Oxime ether formation prevails over Kharasch peroxidation

Oxidative coupling of oxime and β-dicarbonyl compounds dominates in a β-dicarbonyl compound/oxime/Cu(II)/t-BuOOH system; in the absence of oxime, oxidative coupling of t-BuOOH and a β-dicarbonyl compound (Kharasch peroxidation) takes place. The proposed conditions for oxidative coupling of oximes with dicarbonyl compounds require only catalytic amounts of copper salt and t-BuOOH serves as a terminal oxidant. The C–O coupling reaction proceeds via the formation of tert-butoxyl, tert-butylperoxyl and iminoxyl radicals. Apparently, tert-butylperoxyl radicals oxidize oxime into iminoxyl radical faster than they react with β-dicarbonyl compounds forming the Kharasch peroxidation product. Iminoxyl radicals are responsible for the formation of the target C–O coupling products; the yields are up to 77%.