Formation of lead pyrophosphate glass and the role of anion disproportionation

Thermal, spectroscopic and electrical properties of lead pyrophosphate glass prepared by melt quenching have been examined. A model based on the structural disproportionation of the P₂O ₇ ⁴⁻ ions has been proposed and is shown to consistently explain all the observations. The equilibrium of various anionic species has been discussed on the basis of their electronegativities which are in turn related to their basicities. Communication No. 129 from the Materials Research Centre     

相转移催化元素硫的歧化反应

本工作将相转移催化(PTC)应用于元素硫歧化反应,大大降低了反应温度,提高了反应速度。该反应被证实与熔态硫在水溶液中的歧化相同,即4S+6OH~-=2S~(2-)+S_2O_3~(2-)+3H_2O。比较了四乙基铵、四丁基铵、十六烷基三甲基铵和三辛基甲基铵四种相转移催化剂及四氯乙烯、二甲苯和四氯乙烷三种溶剂的影响。讨论了本体系相转移催化的证据。为改进以元素硫歧化反应为基础的提取冶金过程提供了依据。     

Disproportionation of 6,8-Dialkyl-3-thia-2,4,6,8-tetraazabicyclo[3,3,0]octan-7-one 3,3-Dioxides under Conditions of Acid Hydrolysis and Acetylation

Acid hydrolysis and acetylation of 6,8-dialkyl-3-thia-2,4,6,8-tetraazabicyclo[3,3,0]octan-7-one 3,3-dioxides have been studied. 6,8-Dialkyl-3-thia-2,4,6,8-tetraazabicyclo[3,3,0]octan-7-one 3,3-dioxides disproportionate to 4,4'-sulfonyldiiminobis(1,3-dialkylimidazolidin-2-ones) and sulfamide when treated with acid at pH 1 or with acetyl chloride. The kinetics of the disproportionation have been studied.     

Anomalous relationship of the energy of the sequential ionization of molecular systems as a result of effective electron-electron attraction in molecules

Conditions were found, under which an anomalous relationship should be observed in the energies of sequential ionization of molecules ("anomalous" molecules) such that a subsequent potential (I_n+1) is less than the preceding potential (I_n). These conditions are a function of the electronic vibrational instability of molecules or their ions upon change in the number of electrons in the system. An interrelationship was found with the previously proposed concept of effective electron—electron attraction in molecular systems.Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 738–741, March, 1992.     

Bromination of regioisomeric fluorine-containing β-aminovinyl ketones

Bromination of -aminovinyl ketones (AVK) with geminal arrangement of the fluoroalkyl and amino groups gives N-bromo derivatives. Regioisomeric AVK with the amino groups in the -position relative to the fluoroalkyl group undergo bromination under analogous conditions to give a mixture of the -bromo and ,N-dibromo derivatives. -Bromo derivatives of AVK disproportionate upon storage.Division of Fine Chemical Synthesis, Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 620219 Ekaterinburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 746–749, March, 1992.     

MIL⁃53(Al)催化甲基氯硅烷的歧化机理

利用B3LYP/6?311++G(3df,2pd)方法计算了MIL?53(Al)的3个位点催化甲基氯硅烷以制备二甲基二氯硅烷的活性差异,并对反应通道、能量、过渡态虚振模式、内禀反应坐标(IRC)、关键原子间距的变化等进行了分析和讨论,得出了一致的结论:1~3号活性位催化的主反应速控步的活化能分别为157.15、155.31和123.44 kJ·mol-1;副反应速控步的活化能分别为206.48、214.87和166.07 kJ·mol-1。MIL?53(Al)能顺利催化歧化反应的原因在于其催化中心Al—O—H上的Br?nsted酸H,活性的差异来源于其配位环境的不同。     

Towards Single-component Molecular Conductor [Ni(dmit)_2] by Charge Disproportionation:2[Ni(dmit)_2]~(-0.5)[Ni(dmit)_2]+[Ni(dmit)_2]~-

It was commonly thought that a molecular conductor or semiconductor should be composed of at least two components to make the conducting component in partially charged state. However, this idea became questionable by the recent report of the single-component molecular conductor [Ni(tmdt)2]1 as well as several reports about single-component molecular semiconductors such as [Ni(ptdt)2]2 and [Ni(C10H10S8)2]3. In fact, as early as 1985, [Ni(dmit)2] as a by-product in synthesizing TTF[Ni(dmit…     

Polysiloxanol condensation and disproportionation in the presence of a superacid

Kinetics studies of the condensation of model hydroxyl-terminated oligosiloxanes, pentamethyldisiloxane-1-ol (MDH) and heptamethyltrisiloxane-1-ol (MD₂H), catalysed by protic complex of tetrakis(pentafluorophenyl)borate in the toluene solution were performed. The dominating reaction was condensation, which was accompanied by disproportionation of oligosiloxanols. Water released in the condensation forms separate dispersed phase, but the phase separation and the presence of water does not affect the rate of the polycondensation. Both processes, condensation and disproportionation, show analogous kinetic laws being first order in silanol and half order in catalyst. They exhibit also similar values of activation parameters. The kinetics are explained by the formation of a reactive protic complex of silanol with borate being in fast preequilibrium with an unreactive complex including two borate molecules and the silanol molecules. The equilibrium lies to the side of the unreactive borate complex.     

Controlling the duality of the mechanism in liquid-phase oxidation of benzyl alcohol catalysed by supported Au-Pd nanoparticles

In the solvent-free oxidation of benzyl alcohol to benzaldehyde using supported gold-palladium nanoparticles as catalysts, two pathways have been identified as the sources of the principal product, benzaldehyde. One is the direct catalytic oxidation of benzyl alcohol to benzaldehyde by O(2), whereas the second is the disproportionation of two molecules of benzyl alcohol to give equal amounts of benzaldehyde and toluene. Herein we report that by changing the metal oxide used to support the metal-nanoparticles catalyst from titania or niobium oxide to magnesium oxide or zinc oxide, it is possible to switch off the disproportionation reaction and thereby completely stop the toluene formation. It has been observed that the presence of O(2) increases the turnover number of this disproportionation reaction as compared to reactions in a helium atmosphere, implying that there are two catalytic pathways leading to toluene.