Labile Interactions Defined in Crystalline Metal Complexes

The problems involved in identifying and quantifying labile interactions considered to influence complex compound structures are highlighted through the assessment of four different families of metal complexes for which extensive crystallographic data are available. Modification of the charge distribution within a ligand molecule as a result of coordination is one factor with a number of ramifications. A detailed analysis of evidence for both intra- and inter-molecular attractions in dimethylsulfoxide complexes of metal perchlorates is used to provide a basis for the consideration of weak interactions between complex ions involving forces including phenyl-group attractions, hydrogen bonding and cavity inclusion.     

The Isoelectric Point and the Points of Zero Charge of Fe-Al-Mg Hydrotalcite-like Compounds

The relation of the isoelectric point (IEP) and the point of zero net charge (PZNC) of the hydrotalcite-like compounds was discussed. It was found that the IEP does not equal to the PZNC and the IEP is higher than the PZNC. The structural positive charges existing in the HTlc,which cause the difference between the IEP and the PZNC. The effects of the structural positive charges of the HTlc on its IEP and PZNC are the same as the specific adsorption of metal cations.     

MO analysis of macroscopic supercurrent flow in MgB 2

We present results from an extended magneto-optical (MO) analysis of two samples cut from high-density pellets of MgB₂. The first sample was studied in order to show that no matter how large the sample is and despite the bulk granularity, the material enters into a critical state in a crystal-like fashion. The second sample was chosen for the quantitative analysis. A numerical approach based on an inverted 2D Biot-Savart model was used to calculate the current paths across the homogeneous polycrystalline bulk, as well as in the vicinity and across some morphological defects. Local current densities in the homogeneous part were estimated as a function of the applied magnetic field at different temperatures, in three regimes: below full penetration, at full penetration and above full penetration, respectively. A hypothesis of interpretation of the apparent absence of magnetic granularity inside the polycrystalline microstructure is presented. It is related to a critical state likely reached by a network of strongly coupled Josephson junctions. Received 31 May 2001 and Received in final form 5 December 2001     

N-烷基-O-烷基-O-(1,2,2,2-四氯乙基)硫代磷酰胺酯的合成研究

合成了9个未见文献报导的四氯乙基硫代磷酰胺酯,并对它们的合成、结构和性质以及杀蚜虫、线虫活性等进行了初步研究。     

Long range one-dimensional ordering of lead phthalocyanine monolayer on InSb(1 0 0) (4 × 2)/c(8 × 2)

Sub-monolayer and monolayer of lead phthalocyanine deposited on InSb(1 0 0) (4 × 2)/c(8 × 2) surface have been investigated by scanning tunneling microscopy and low energy electron diffraction. Molecules first adsorb on the indium rows of the (4 × 2)/c(8 × 2) structure in the [1 1 0] direction and diffuse at the surface in order to form two-dimensional islands. The molecule-substrate interaction stabilizes the PbPc molecules on the In rows. It weakens the interaction between molecules located in adjacent rows resulting in numerous gliding planes between the molecular chains, in the direction parallel to the rows. At monolayer completion, a long-range one-dimensional order is adopted by the molecules in the [1 1 0] direction.     

Chemical reactivity of hypervalent silicon compounds: The local hard and soft acids and bases principle viewpoint

The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of the silicon atom for SiH _n F_4−n and SiH _n F _5−n ¹⁻ . The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft nucleophiles preferably react with SiH _n F _5−n ¹⁻ , and hard nucleophiles with SiH _n F_4−n .     

An effect of application of chiral aluminium alkoxides and amides as adducts to zirconium catalyzed carbo- and cycloalumination of olefins

This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt₃ and i-Bu₂AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp₂ZrCl₂.     

The analysis of volatile trace compounds in landfill gases,compost heaps and forest air

Landfill gas, cryotrapped on a loop fashioned from a length of a capillary gas chromatography (GC) column, was examined for volatile organometallic compounds (VOMCs) and for volatile organic compounds (VOCs) by using GC–mass spectrometry (MS). A large number of organic components were present and many were identified, but the only VOMCs present in high enough concentrations to be detected were trimethylstibine and tetramethyltin. The use of inductively coupled plasma (ICP)‐MS as an element‐specific detector allowed the identification of a number of other organometallic species in the landfill gas, including trimethylarsine and trimethylbismuth, and, for the first time, butyltrimethyltin and dibutyldimethyltin. The presence of molybdenum hexacarbonyl was confirmed. Gas from a large‐scale compost heap and from compost incubated in the laboratory contained iodomethane but no common VOMCs (GC–ICP‐MS). Only VOCs were present in forest air (GC–MS). Copyright © 2003 John Wiley & Sons, Ltd.     

贝壳固硫过程热重研究

利用LCT-2型热天平对贝壳的固硫反应过程进行了实验研究。探讨了贝壳在含SO2模拟烟气气氛下的固硫能力、温度特性及SO2浓度对其钙利用率的影响特性;并利用JXA-840扫描电镜实验观察了贝壳与石灰石微观结构特性的主要差别。结果表明:贝壳具有良好的微观结构特性和固硫反应活性,其最佳固硫反应温度比石灰石高出约100℃,大部分贝壳更适合作900~1000℃温度下的燃煤固硫剂。