Dissipative extensions of a symmetric relation generated by a system of integral equations with operator measures

With the help of boundary conditions we describe dissipative and accumulative extensions of the minimal relation generated by a system of integral equations with operator measures in an infinite-dimensional case.     

Conjugate reactions: New potentials of an old idea

Main concepts of the Shilov–Ostwald theory of conjugate chemical reactions are analyzed from the standpoint of complex reaction kinetics, theory of reaction routes, and thermodynamics of irreversible processes. Classification of conjugate reactions and an algorithm of catalytic system design for conducting these processes are proposed.     

Analogs of pyrimidine nucleosides

N₁-(-Tetrahydrofuranyl)- and N₁-(-tetrahydropyranyl)uracils and the corresponding 6-azauracils have been obtained by the condensation of bistrimethylsilyl derivatives of uracils and 6-azauracils with-chlorotetrahydrofuran and-chlorotetrahydropyran. The superiority of the silyl method over the mercury method used previously has been demonstrated.For part III, see [9].     

The mechanism of formation and some properties of thin fluorocarbon films deposited onto silicon plates by electron-beam polymerization of hexafluoropropylene from the vapor phase

The results of studying thin fluorocarbon films deposited onto single-crystal silicon plates through electron beam polymerization of hexafluoropropylene from the vapor phase are presented. The films are deposited under the action of an electron beam with an energy of 40 keV at a monomer vapor pressure of 5- 20 hPa. It is shown that plastic solid films consisting of a low-molecular-mass polymer with low thermal stability are formed at a beam current density on the order of 20 μA/cm², while at current densities on the order of 150 μA/cm², rigid brittle films of three-dimensional crossl inked polymer are formed with a thermal stability of about 350°C. It is assumed that the films are formed via chain polymerization, which at high current densities, is accompanied by polyrecombination processes leading to efficient chain crosslinking. It is found that polymer clusters are ordered in the course of film formation.     

Palladium(<Emphasis Type="SmallCaps">I</Emphasis>) and palladium(0) carbonyl bromide complexes

New Pd^I and Pd⁰ carbonyl bromide complexes co-existing in the same crystal were synthesized and studied by X-ray diffraction analysis. The crystals consist of dimeric complex anions composed of the central Pd(μ-CO)₂Pd fragment and four partially disordered terminal ligands (CO and Br⁻). The complexes were characterized by IR, ESR, and X-ray photoelectron spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1349–1355, June, 2005.     

Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene. Generation and experimental discrimination of hypotheses

Formal and informal methods for advancing hypotheses on mechanisms were used in a study of the oxidative carbonylation of phenylacetylene to methyl phenylpropiolate catalyzed by the PdCl₂−CuCl−CuCl₂ system. The hypotheses remaining after discrimination and consistent with all experimental data include the steps of formation of the Cu^I alkynyl complex, transfer of the phenylethynyl group from Cu^I to Pd^II, insertion of carbon monoxide into a Pd−C or Pd−OMe bond of the Pd^II σ-alkynyl complex. Comparison of the formal and informal methods for advancing hypotheses confirmed a higher effeciency of the first method. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 882–889, May, 1999.     

New catalytic systems for oxidative carbonylation of acetylene to maleic anhydride

A classification of polyfunctional catalytic systems based on discrimination of the main component (the catalyst participating in all stages of the formation of the product of catalytic reaction) and elucidating the functions of additional components of a catalytic system is suggested. The role of additional components in a number of new palladium-based catalytic systems used in the synthesis of maleic anhydride by oxidative carbonylation of acetylene was studied. It was established that the functions of Co and Fe phthalocyanine complexes (PcCo and Pc^*Fe, respectively) in the mechanism of the process are different. Translated fromIzvestia Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1899–1905, October, 1999.     

On linear relations generated by an integro-differential equation with Nevanlinna measure in the infinite-dimensional case

A system of integral equations that can be reduced to an integro-differential equation with Nevanlinna measure is considered. The families of maximal and minimal linear relations are defined and their holomorphy is established. It is proved that the operators inverse to continuously invertible restrictions of the maximal relations are integral.