Kinetic Equations for Thermal Dissociation Processes. Part I. KEKAM equation

Relationships have been established between the average conversion degree and the dissociation time for polydisperse granular material, taking its grain size distribution into account. It has been checked in which cases the kinetic curves obtained by a numerical solution can be described in terms of KEKAM equation. This revised version was published online in August 2006 with corrections to the Cover Date.     

分子筛模型中非骨架离子位置的研究

从理论上研究了非骨架阳离子可能的分布位置．计算了分子筛晶体基本结构单元在整个空间的静电势分布，找出空间中静电势的各个极小点．在静电势最低点逐个放置钠离子，优化，重新计算模型分子筛的电势分布．研究了阳离子放置过程中静电势变化的趋势．     

Neue Pyridiniumchlorometallatverbindungen der Seltenerdelemente

Summary Reaction of the rare earth chlorides with pyridinium chloride in tetrahydrofuran (THF) under anhydrous conditions gave nearly insoluble precipitates of the composition (pyH)₃ RECl₆·THF (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, and Lu). They were characterized by chemical analysis and IR spectroscopy; decompositionin vacuo was studied, yielding the hithero unknown complexes (pyH)₃ RECl₆ (RE=La, Ce, Pr, Sm, Tb, Ho, Y, Tm, and Lu).

     

Geometry,stability and aromaticity of β-diketiminate-coordinated alkaline-earth compounds

Alkaline-earth (Ae) metals have attracted a wealth of interdependent research from synthetic chemists. In Ae-catalyzed organometallic reactions, β-diketiminate is a typical ligand used to stabilize Ae catalysts by forming six-membered rings comprising Ae metals. Herein, studies focusing on the configuration of β-diketiminate-coordinated Ae compounds observed that the CC and CN bonds are homogeneous and unchanged. Furthermore, energetic studies observed that the formation of the Ae-incorporated six-membered rings results in enhanced stability of >20 kcal/mol. The nucleus-independent chemical shifts, anisotropy of the induced current density, and molecular orbital analyses demonstrated the non-aromaticity of the β-diketiminate-coordinated Ae compounds. The improved stability of these compounds can be explained by the delocalization of the π electrons derived from the β-diketiminate moiety.     

Siloxane-Based Nanobuilding Blocks by Reaction Between Silanediol and Trifunctional Silicon Alkoxides

The preparation of nanostructured organic-inorganic materials by assembling of nanobuilding blocks allows controlling the extent of phase interaction, which in its turn governs structure-properties relationships. We present here the synthesis of siloxane-based nanobuilding blocks prepared by reacting diphenylsilanediol with vinyltriethoxysilane and triethoxysilane. The reaction products were obtained by non-hydrolytic condensation between silanediol and ethoxide groups in inert atmosphere, in the presence of pyridine, triethylamine or butyl lithium. Different synthetic conditions were examined by means of ATR-FTIR and NMR spectroscopies, showing the formation of siloxane bonds. In the case of triethoxysilane the reaction carried out in the presence of pyridine leads to Si–H bond preservation in the final product. Air stable products with improved Si–O–Si hydrolytic stability can be obtained by removal of the base after the reaction completion. The condensation products can be described as a mixture of siloxane rings involving difunctional and trifunctional silicon units.     

Recyclization of 1,4-dihydropyridine derivatives in acidic medium

The recyclization of 1,4-dihydropyridines in aqueous-alcoholic hydrochloric acid medium proceeds with cleavage of a C-N bond and pyridine ring opening. Cyclohexenone derivatives are formed as a result of the subsequent intramolecular crotonic condensation of the acyclic intermediate. The leaving carbonyl substituents depart simultaneously with recyclization, depending on the acidity of the reaction medium. Dedicated to Prof. Dr. E. Lukevics on the occasion of his 70th birthday. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 49–58, January, 2007.     

Manifestation of diamagnetic chemical shifts of proton NMR signals by an anisotropic shielding effect of nitrate anions

A remarkable upfield shift of the py_α protons of complexed 2,2′-bipyridine in [cis-Pd(bpy)(NO₃)₂] is observed which is considered to originate from the anisotropic influence of suitably positioned coordinated nitrate anions around the Pd(II) centre of the molecule. A typical complexation-induced downfield shift is observed for the NH₂ protons in [cis-Pd(en)(NO₃)₂] where ‘en’ stands for ethylenediamine.     

Equilibrium studies of Mn(II), Mg(II), Ca(II), Sr(II) and Ba(II) withp-fluoro-,p-chloro-,p-bromo-,p-methyl-benzoylacetones and 1-(4-fluorophenyl)-1,3-pentanedione

The rawpH-data, obtained from the potentiometric titrations of the titled ligands with NaOH in 75% (v/v) dioxane-water mixture performed at 20, 30 and 40°C at constant ionic strength (=0.1M-NaClO₄), have been adequately corrected for dilution, and solvent effects in order to evaluate thermodynamic dissociation constants. Variance of the latter as a function of temperature has also been accounted for. The differing magnitudes of thermodynamic dissociation constants of the titled ligands have been explained on the basis of the non coplanar orientation of the phenyl ring in the ligands and a comparison has been made with those of unsubstituted benzoylacetone, dibenzoylmethane and acetylacetone.Following similar technique, thermodynamic stepwise and overall formation constants of the titled metal-ligand systems have been obtained and the results correlated with ligand basicity inverse metal crystal radii and second potentials of metals. Decrease in the free enthalpy (–G) of complexation reaction has also been evaluated.

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Untersuchung der Gleichgewichte von Mn(II), Mg(II), Ca(II), Sr(II) und Ba(II) mit p-Fluor-, p.-Chlor-, p-Brom-, p-Methyl-benzoylaceton und 1-(4-Fluorphenyl)-1,3-pentanedion

Zusammenfassung Aus der potenitometrischen Titration der Titelverbindungen mit NaOH in 75 (v/v) Dioxan—Wasser bei, 20, 30 und 40°C bei konstanter Ionenstärke (=0,1M-NaClO₄) wurden die thermodynamischen Dissoziationskonstanten ermittelt. Verdünnungs-, Lösungsmittel-und Temperatureffekte wurden berücksichtigt. Die unterschiedlichen Dissoziationskonstanten werden mit der Nichtplanarität des Phenylrings in den Liganden erklärt. Außerdem wurden die Komplexbildungskonstanten bestimmt; sie sind in die Diskussion miteinbezogen.

     

Voltage-Height Spectroscopy in the <Emphasis Type="Italic">Ex Situ</Emphasis> Configuration of a Scanning Tunneling Microscope

Basic regularities of electrochemical processes in the gap of an ex situ scanning tunneling microscope in conditions of condensation of air moisture at the sample surface are considered on a qualitative level. A layer of condensed moisture is viewed as an electrolyte in a two-electrode cell. The depolarizers present in this layer may experience electrochemical conversions on the tip and in an area of the sample surface near the tip. As a result, the recorded “tunneling” current includes electrochemical constituents. Depending on the electrochemical processes in the gap, various dependences of the tip-sample distance on the current and applied voltage can be expected. For preliminary diagnostics of processes in the gap it is suggested to use voltage-height spectra, whose shape and characteristic heights are sensitive to the nature and location of redox active species. Experimental data for various films on conducting supports (quasi-two-dimensional adsorbed layers of hemin and peroxidase, electrodeposited nonstoichiometric tungsten oxides, doped tin dioxide, solid electrolyte with ionic conduction) are presented as an examples.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 583–595.Original Russian Text Copyright © 2005 by Yusipovich, Vassiliev.