配位化学的创始与现代化

本文扼要介绍了韦尔纳配位理论的第一篇文章的内容，讨论了配位化学的发展和现代化。配合物稳定性决定于多种作用力与组分间的互补性和拓扑约束性。     

Ga8Ir4B – ein Gallium-Iridiumborid mit isolierten,annähernd quadratisch planaren Ir4B-Gruppen in einer vom CaF2-Typ abgeleiteten Struktur

Ga₈Ir₄B – a Gallium Iridium Boride with isolated, nearly square planar Ir₄B Groups in a Structure derived from the CaF₂ Type The new compound Ga₈Ir₄B (tetragonal, I4₁/acd, a = 853.69(2) pm, c = 2 105.69(6) pm, Z = 8, 614 reflections, 31 parameters, R = 0.034) was prepared by reaction of the elements at 1 100°C. The structure is derived from the CaF₂ type. It contains isolated Ir₄B groups with boron in an unusual, nearly square planar coordination.     

Vacuum Ultraviolet Photolysis of Polyethylene,Polypropylene, and Polystyrene

Using infrared reflection absorption spectroscopy (IRRAS), quartz crystal microbalance (QMB) measurements, and X-ray photoelectron spectroscopy (XPS) in combination with chemical derivatization techniques the VUV photolysis of polyethylene (PE), polypropylene (PP), and polystyrene (PS) was investigated. A mass balance obtained from the quantification of the data was used to suggest reaction path ways. Although PE and PP behave similar, the mass loss is about 8 times higher in the case of PP. These differences originate from the higher disproportionation to recombination ratio for the branched polymer. Both polymers form double bonds and at extended treatment times they tend to crosslink. PS is rather stable due to the possibility of the energy dissipation by fluorescence.     

热致性液晶聚酯酰亚胺高分子的合成

本文以己二胺，癸二胺和对－亚苯基－双苯偏三酸酯二酐为单体通过溶液聚合反应制备了聚酯酰亚胺系列共聚物．采用ＩＲ，ＷＡＸＤ，ＤＳＣ和偏光显微镜研究了共聚物的结构和液晶性能，结果表明，聚合物具有热致液晶性，且随二胺单体摩尔组成的变化，共聚物的熔点Ｔｍｌ和玻璃化转变温度Ｔ８呈规律性变化．     

Crystal and molecular structure of a 1:1 complex of a chiral α-d-glucosido-benzo-18-crown-6 and potassium thiocyanate

C₂₈H₃₆O₁₀. KSCN is monoclinic, space groupP2₁ withZ=2,a=10.390(3),b=8.959(7),c=16.377(7) Å, =92.49(5)°. FinalR=0.053 for 1437 reflections measured at room temperature. The K^– ion lies on the least-squares plane formed by the six oxygen atoms in the macrocyclic ring. The SCN^– ion was found on the same face of the macrocycle as the chiral glucopyranoside moiety.Methyl-4,6-O-benzylidene-2,3-O-(1,2-bis(ethoxyethoxy)benzenediyl)--d-glucopyranoside.     

四甲基锡在MCM-41分子筛表面的接枝反应及产物性能

研究了真空条件下SnMe4在MCM-41分子筛表面的接枝反应，并用元素分析、ICP、GC-MS、XRD、FTIR、DRS、13C及119Sn MAS NMR、XPS、BET、TPD、TPR等方法对产物的组成、结构和性质进行了表征.结果表明, 两者可以定量地进行化学反应，将确定数目的甲基锡基团接枝在分子筛表面, 形成SnMe3/MCM-41物种；接枝反应发生在分子筛表面上, 不破坏MCM-41分子筛骨架结构；改性分子筛的BET比表面积有所降低，孔体积变小, 表面性质发生变化.四甲基锡在MCM-41上接枝反应的温度为343 K,比它与HY沸石的反应温度(193 K)高得多，并且产物SnMe3/MCM-41的热稳定性也高于SnMe3/HY.     

PRIRODA-04: a quantum-chemical program suite. New possibilities in the study of molecular systems with the application of parallel computing

Main characteristics are described of the PRIRODA quantum-chemical program suite designed for the study of complex molecular systems by the density functional theory, at the MP2, MP3, and MP4 levels of multiparticle perturbation theory, and by the coupled-cluster single and double excitations method (CCSD) with the application of parallel computing. A number of examples of calculations are presented.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 804–810, March, 2005.     

尿嘧啶-BH3复合物构型与性质的MP2理论研究

用MP2方法在6—31G基组水平对尿嘧啶-BH3复合物进行了理论计算，以预测该复合物的构型及稳定化能，得到了5种构型，对各构型进行了振动频率分析和自然键轨道分析．结果表明，B与O直接结合的构型比较稳定，其稳定化能分别为95．5和93．4kJ／mol．各种构型都存在不同程度的电荷转移，转移方式和转移量与结合方式有关．复合物的形成使红外光谱中的N-H键，B-H键和C-O键的伸缩振动频率均有所降低．     

Acetylenic/cyanoacetylenic complexes: simulation of the Titan’s atmosphere chemistry

The structures and energies of the 1:1 acetylene/cyanoacetylene, acetylene/dicyanoacetylene and cyanoacetylene/dicyanoacetylene complexes in solid argon matrices have been investigated using FT-IR spectroscopy and ab initio calculations, at the B3LYP/6-31G** level of theory. For the three complexes, predicted frequency shifts for the L shaped structures, characterized by a hydrogen bond between the nitrogen of the cyano group and the acetylenic proton, were found to be in good agreement with those experimental. Only in the case of acetylene/cyanoacetylene complex, we obtained a second minimum with a T shaped structure characterized by an interaction between the proton of cyanoacetylene and the Π system of acetylene. It appears clearly that HC₃N acts as an electrophile or as a nucleophile in these complexes.     

Phase Equilibria and Crystal Structure of Complex Oxides in the La–Sr–Co–Ni– System

Phase equilibria in the La–Sr–Co–Ni–O system were studied in air at 1100°. The samples for the study were synthesized by the standard ceramic and citrate processes. The limiting solubility and structure of La_1-xSr_xCo_1-yNi_yO_3- and (La_1-xSr_x)₂Co_1-yNi_yO₄ solid solutions were determined by Xray powder diffraction analysis. La_1-xSr_xCo_1-yNi_yO₃- solid solutions with 0 x 0.5 have a distorted rhombohedral perovskitelike structure (R c space group). An increase in the strontium concentration reduces the rhombohedral distortions, and the compounds with x < 0.5 have an ideal cubic structure (Pm3m space group). (La_1-xSr_x)₂Co_1-yNi_yO₄ crystals have a tetragonal K₂NiF₄ type unit cell (I4/mmm space group). The relationships between unit cell parameters and compositions were obtained for singlephase La_1-xSr_xCo_1-yNi_yO_3- and (La_1-xSr_x)₂Co_1-yNi_yO₄ samples. The existence regions of La_1-xSr_xCo_1-yNi_yO₃- and La_1-xSr_x)₂Co_1-yNi_yO₄ solid solutions were distinguished on P–T phase diagrams.