Formation of high-spin complexes in reactions of oxides of the γ-Al2O3 type with radical pairs of sterically shielded semiquinones: A new procedure for the preparation of organometallic polyradicals and their ESR spectra

A new simple method was developed for the preparation of organometallic bi- and triradicals by the heterogeneous reaction of γ-Al₂O₃ or analogous oxides with free radicals generated in solution through the interaction of 3,6-di-tert-butyl-o-benzoquinone with 3,6-di-tert-butylpyrocatechol. An explanation was offered for the plus sign of the dipoledipole coupling constant observed previously in the ESR spectra recorded in a superstrong field at low temperatures. Deceased. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 298–302, February, 1997.     

Evidence of lanthanum–chromium mixed oxides formed in CrOx/La2O3 model catalysts

CrO_x/La₂O₃ mixed oxides, prepared by impregnating La₂O₃ with appropriate aqueous solutions of (NH₄)₂CrO₄ and calcining at 600 °C for 4 h, have been investigated by means of XRD, TPR, XPS, DRIFTS, and Raman spectroscopy (RS). The formation of the compounds La₂CrO₆, La(OH)CrO₄ and LaCrO₄ under these conditions was evidenced. Strong peaks at 864, 884, 913, and 921 cm⁻¹, as well as weak peaks at 136, 180, 354, 370, and 388 cm⁻¹ in the RS spectrum of CrO_x/La₂O₃ have been assigned to La₂CrO₆.     

Electrochemical properties and state of paramagnetic centers in copper-modified complex vanadium and titanium oxides

Complex vanadium and titanium oxides modified by copper ions are studied by the electrochemical and ESR methods. Oxides Cu _x V_2?y Ti _y O_5?δ·nH₂O (0<y<1.33) have a layered structure and oxides Cu _x Ti_1?y V _y O_5+δ·nH₂O (0<y<0.25), an anatase structure. The intercalation of cations Cu²⁺ into the hydrates leads to oxidation of V⁴⁺. According to ESR data, V⁴⁺ exists in the oxides in the form of VO²⁺ and an octahedral surround of oxygen (V⁴⁺?O₆), respectively. The electroreduction of ions of d-elements and chemisorbed oxygen in the oxides is analyzed. The intercalation of cations Cu²⁺ alters the content of V⁴⁺ and the chemisorption ability of the oxides. Possible reasons for this phenomenon are discussed.     

Theoretical exploration of structure-reactivity relationships in organometallic chemistry: butadiene insertion into the organyltransition-metal bond and conversion of the allyltransition-metal fragment in the [Ni(η-Cp)(η-phenyl)(η-butadiene)] complex

We have theoretically examined the reaction course of the butadiene insertion into the arylNi^II bond in the [Ni^II(η⁵-Cp)(η¹-phenyl)(η²-butadiene)] complex (1), by employing a gradient-corrected DFT method. Critical elementary processes have been scrutinized, viz. monomer insertion, rotational allylic isomerization and allylic η¹-σ→η³-π rearrangement. The first mechanism suggested by Lehmkuhl et al. was refined and supplemented with important details. The critical factors that determine the generation of anti-η³- and syn-η³-allyl isomers of the [Ni^II(η⁵-Cp)(1-benzyl-allyl)] product have been elucidated. This let us to rationalize the experimentally observed, almost exclusive formation of the anti-η³-allyl isomer. Butadiene preferably inserts in η²-mode into the η¹-phenylNi^II bond, initially giving rise to the η¹(C³)-allyl product species, 3σ. The direct formation of the η³-allyl product species, 3π, along the alternative path for η⁴-butadiene insertion, however, is found to be almost entirely disabled kinetically. The thermodynamically favorable η²-trans form of 1 is also shown to be more reactive in accomplishing CC bond formation. Species 3σ is indicated to be a metastable intermediate, occurring in an appreciable stationary concentration. Its respective anti and syn isomeric forms are likely to be in equilibrium, due to the facile rotational isomerization. The subsequent allylic rearrangement into the thermodynamically strongly favorable η³-allylNi^II coordination mode is shown to be the crucial elementary step that discriminates which of the isomeric η³-allyl forms is preferably generated. The higher reactivity of the anti isomer in this process decisively determines the almost exclusive formation of the anti-η³-allyl product species under kinetic control. The requirement of elevated temperatures for the anti-η³-allyl→syn-η³-allyl isomerization to occur, as revealed from experiment, is attributed to the pronounced thermodynamic stability of the η³-allylNi^II coordination.     

An FT-IR study of adsorption of sulfur dioxide on alpha- and gamma-alumina

In the Claus process hydrogen sulfide reacts to elemental sulfur. Because the Claus reaction is thermodynamically limited, sulfur compounds are still present in Claus tailgas. To avoid air pollution, the tailgas has to be treated.Alfa- and gamma-alumina are being used either as a catalyst or as a support for an active component in the Claus process and some tailgas treatment processes. In order to elucidate the mechanism of the Claus reaction, the adsorption of sulfur dioxide on both of the above aluminas was investigated using Fourier transform infrared spectroscopy.Different adsorbed species displaying a different heat of adsorption were detected. A broad band near 3500 cm^–1 is associated with the basic hydroxyl groups. This band is assigned to a hydrogen bond between the surface of alumina and a bisulfite species. As bisulfite species are reactive towards hydrogen sulfide, we assume that bisulfite species are active intermediates on alumina in the Claus reaction.     

锂离子电池锡氧化物基负极材料的湿化学合成与电化学性质

采用新兴的湿化学方法合成了锡氧化物基粉末材料。用X-射线衍射、扫描电镜和电化学方法对材料的微观结构、形貌和电化学性能进行了详细的研究。结果表明，经400 ℃热处理4 h的锡氧化物基材料的颗粒大小均匀，平均粒径约为200 nm。这种材料的可逆充电容量超过570 mAh·g^-1，30次循环后平均每次循环的容量衰减只有0.15%。良好的电化学性能表明锡氧化物基材料有望作为新一代锂离子电池的负极材料。     

Solidification of metallic tin in dispersed phase

Differential scanning calorimetry (DSC) and particle size measurements were carried out on disproportionation products of pure SnO to investigate the fusion and solidification behaviour of Sn droplets and their catalytic nucleation on Sn oxides. If disproportionation reaction takes place at T ≥ 798 K, the products are metallic Sn and SnO₂; but for 523 < T < 798 K, SnO₂ is replaced by an intermediate oxide (IO) Sn_xO_(1+x). On melting, samples with IO show a drop of melting point of metallic tin due to Gibbs–Thomson effect; no lowering of melting point was observed in samples with SnO₂. On the other hand, if solidification occurs in the presence of IO, Tin droplets always displayed three distinct exothermic solidification peaks, but if it takes place in the presence of SnO₂, only one exothermic peak is observed. Undercooling values and contact angles were determined for each of the heterogeneous nucleation processes. The different behaviour of metallic Tin droplets was related to the different lattice symmetry of SnO₂ and IO, which act as nucleation catalysts.     

Ln2O3/Al2O3催化酯化合成邻苯二甲酸二辛酯

Ｌｎ_２Ｏ_３／Ａｌ_２Ｏ_３催化酯化合成邻苯二甲酸二辛酯陈其瑞，张凤美，罗明润，焦肇林（安徽师范大学化学系，芜湖２４１０００）关键词稀土氧化物，担载催化剂，催化酯化，邻苯二甲酸二辛酯邻苯二甲酸二（２－乙基己醇用酯（Ｄｉｏｃｔｙｌｐｈｔｈａｌａｔｅ）是一...     

Thermolysis of furoxans annulated with five-membered carbocycles in the presence of dipolarophiles

The conditions for the thermolysis of furoxans annulated with differently strained five-membered carbocycles (cyclopentafuroxan 1, norbornenofuroxan 2, and acenaphthofuroxan 3) to bis(nitrile oxides) in the presence of various dipolarophiles (diethyl acetylenedicarboxylate, benzoylformonitrile, and ethoxycarbonylformonitrile) were optimized. It was found that the reactivities of the above furoxans as sources of bis(nitrile oxides) decrease in the order 2 > 1 > 3. Among the furoxans studied, only norbornenofuroxan 2 can be recommended as a possible cross-linking reagent for polymers. The formation of di-N-oxides of 3,4-bis(cyanopropyl)-, 3,4-bis(cyanocyclopentyl)-, and 3,4-bis(cyanonaphthyl)furoxans was detected. They resulted from intermolecular cyclodimerization of bis(nitrile oxides) initially formed in the thermolysis of furoxans 1–3. Dedicated to Academician V. A. Tartakovsky on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1521–1528, August, 2007.