Behavior of 1-hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide and the corresponding nitroxyl radicals in superacid media

The protonation of 1-R-2,2,5,5-tetramethyl-3-imidazoline-3-oxides (R=OH, O) in superacid media was investigated with¹H and¹³C NMR. The hydroxylamino dication forming on protonation can undergo imidazoline ring opening to form an isomeric mixture of diprotonated N-(2-hydroxyimino-1,1-dimethylethyl),,-dimethylnitrones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2755–2761, December, 1991.     

The first example of the generation of carbocations by the protonation of unsaturated compounds by a CH acid

The protonation of unsaturated organic compounds is one of the general methods for the generation of carbocations. Strong Brönsted acids in which a hydrogen atom is attached directly to an atom having high electronegativity (O, Hal) are usually employed for this purpose. We found that CH acids can also be used for the generation of carbocations.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1231–1232, May, 1991.     

Influence of substituents and cooperativity in doubly hydrogen-bonded complexes of 2-pyridone and oxalic acid

We performed a systemic investigation of the substitution and cooperative effects on the O–H···O and N–H···O H-bonds in the complexes of 2-pyridone and its derivatives with oxalic acid. Generally, the electron-withdrawing substituent in 2-pyridone weakens the O–H···O H-bond but strengthens the N–H···O H-bond, while the opposite effect is for the electron-donating group. In addition, the substitution effect is associated with its substitution position in 2-pyridone. The total interaction energy of a chainlike trimer with oxalic acid as a middle molecule exhibits some additivity. When oxalic acid combines with two 2-pyridone/2-pyridinethione molecules, the O–H···O/S H-bond is weakened but the N–H···O H-bond is enhanced. When three oxalic acid molecules are linked by the double O–H···O H-bonds, one H-bond with the middle oxalic acid as the proton donor is weakened and the other H-bond with the middle oxalic acid as the proton acceptor is strengthened.     

Electrode layers in flows of an inviscid plasma with good conductivity

The structure of the electromagnetic electrode layers that are produced in flows across a magnetic field by a completely ionized and inviscid plasma with good conductivity and a high magnetic Reynolds number is examined in a linear approximation. Flow past a corrugated wall and flow in a plane channel of slowly varying cross section with segmented electrodes are taken as specific examples. The possibility is demonstrated of the formation of nondissipative electrode layers with thicknesses on the order of the Debye distance or electron Larmor radius and of dissipative layers with thicknesses on the order of the skin thickness, as calculated from the diffusion rate in a magnetic field [2].In plasma flow in a transverse magnetic field, near the walls, along with the gasdynamie boundary layers, which owe their formation to viscosity, thermal conductivity, etc. (because of the presence of electromagnetic fields, their structures may vary considerably from that of ordinary gasdynamic layers), proper electromagnetic boundary layers may also be produced. An example of such layers is the Debye layer in which the quasi-neutrality of the plasma is upset. No less important, in a number of cases, is the quasi-neutral electromagnetic boundary layer, in which there is an abrupt change in the frozen-in parameter k=B/p (B is the magnetic field and p is the density of the medium). This layer plays a special role when we must explicitly allow for the Hall effect and the related formation of a longitudinal electric field (in the direction of the veloeiryv of the medium). We will call this the magnetic layer. The magnetic boundary layer can be dissipative as well as noudissipative (see below). The dissipative magnetic layer has been examined in a number of papers: for an incompressible medium with a given motion law in [1], for a compressible medium with good conductivity in [2], and with poor conductivity in [3]. In the present paper, particular attention will be devoted to nondissipative magnetic boundary layers.     

稀土3，4-呋喃二甲酸，1，10-二氮杂菲配合物的光物理性质

研究了稀土Ｇｄ３＋、Ｅｕ３＋、Ｔｂ３＋的３，４呋喃二甲酸，１，１０二氮杂菲（Ｐｈｅｎ）配合物的合成、红外光谱、紫外光谱及光物理性质。详细讨论了配合物的分子内能量传递过程。发现分子内能量传递效率依赖于稀土中心离子的共振发射能级与配体最低三重态能级之间的相对位置。     

Bimetallic single-source precursors [M(NH3)4][Co(C2O4)2(H2O)2]·2H2O (M = Pd, Pt) for the one run synthesis of CoPd and CoPt magnetic nanoalloys

All the steps of the proposed technique, from the synthesis of single-source precursors to the preparation of CoPd and CoPt nanoalloys, are described. The double complex salts (DCS) [M(NH₃)₄][Co(C₂O₄)₂(H₂O)₂]·2H₂O (M = Pd, Pt), which were synthesized by mixing solutions containing [M(NH₃)₄]²⁺ cations and [Co(C₂O₄)₂(H₂O)₂]²⁻ anions, have been used as precursors. The salts obtained were characterized by IR spectroscopy, thermal analysis, XRD and single crystal X-ray diffraction. The prepared compounds crystallize in the monoclinic (space group I2/m, M = Pd) and orthorhombic (space group I222, M = Pt) crystal systems. Thermal decomposition of the salts in helium or hydrogen atmosphere at 200-600 °C results in the formation of nanoalloys powders (random solid solution Co_0.50Pd_0.50 and chemically ordered CoPt). The size of the bimetallic particles varied from 5 to 20 nm. Order-disorder structural transformations in Co_0.50Pt_0.50 nanoalloys were studied. The magnetic properties of both chemically disordered Co_0.50Pd_0.50 and ordered CoPt clusters have also been measured.     

Low-temperature oxidation of carbon monoxide on Pd(Pt)/CeO2 catalysts prepared from complex salts

Catalysts containing cerium oxide as a support and platinum and palladium as active components for the low-temperature oxidation of carbon monoxide were studied. The catalysts were synthesized in accordance with original procedures with the use of palladium and platinum complex salts. Regardless of preparation procedure, the samples prepared with the use of only platinum precursors did not exhibit activity at a low temperature because only metal and oxide (PtO, PtO₂) nanoparticles were formed on the surface of CeO₂. Unlike platinum, palladium can be dispersed on the surface of CeO₂ to a maximum extent up to an almost an ionic (atomic) state, and it forms mixed surface phases with cerium oxide. In a mixed palladium-platinum catalyst, the ability of platinum to undergo dispersion under the action of palladium also increased; as a result, a combined surface phase with the formula Pd _x Pt _y CeO_{2 ? δ}, which exhibits catalytic activity at low temperatures, was formed.     

Crystal structure and thermal properties of [Au(en)<Subscript>2</Subscript>]<Subscript>2</Subscript>[Cu(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>·8H<Subscript>2</Subscript>O

The crystal structure of a double complex salt of the composition [Au(en)₂]₂[Cu(C₂O₄)₂]₃·8H₂O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C₂₀H₄₈Au₂Cu₃N₈O₃₂ are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) ų, P2₁/c space group, Z = 2, d _x = 2.450 g/cm³. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au_0.4Cu_0.6.