DL-PhEtSiIndCpYbCl的合成及表征

以苯基三氯硅烷为原料,先后与乙基溴化镁、茚基锂、茂基锂反应,制备了苯基乙基茚基茂基硅烷(PhEtSiIndCp)。以此为配体与正丁基锂BuLi反应生成二锂盐,再与YbCl3反应,生成苯基乙基硅基桥联茚基茂基镱一氯化物(PhEtsiIndcpYbcl),其结构经^1HNMR,IR,Ms及元素分析表征。     

β－烷氧羰乙撑基三氯化锡与N－芳基－2－羟基乙酰苯叉亚胺配合物的NMR谱与结构

测定了１２个新合成的有机锡－Ｓｃｈｉｆｆ碱配合物的１ＨＮＭＲ谱和１３ＣＮＭＲ谱．详细研究了化合物结构与ＮＭＲ谱的关系．通过比较配体和配合物的ＮＭＲ谱，得出配合物是通过酚羟基氧原子和锡原子的配键生成的．     

Zum chemischen Transport von Yttriumtrichlorid mit Aluminiumtrichlorid

Chemical Transport of Yttrium Trichloride by Aluminium Trichloride Yttrium trichloride is transported by gaseous aluminium trichloride in the temperature range of 300°C to 700°C from hot to cold. It is followed a gaseous complex YAl₄Cl_15,g and the enthalpy of formation as well as the standard entropy of the complex from the dependence of the transport rate on the temperature and the initial pressure of Al₂Cl_6,g.     

DyCl3-CdCl2-H2O和DyCl3-CdCl2-HCl-H2O(25 ℃)的相平衡

测定了三元体系DyCl₃-CdCl₂-H₂O和四元体系DyCl₃-CdCl₂-HCl(～8%)-H₂O(25 ℃)的相平衡溶度数据，绘制了相应的溶度图。三元体系和四元体系均为复杂体系且均有新化合物9CdCl₂·2DyCl₃·29H₂O生成。对化合物9CdCl₂·2DyCl₃·29H₂O进行了XRD、TG-DTG和荧光光谱研究，并对X-射线粉末衍射数据进行了指标化。该化合物属单斜晶系，具有一定的荧光强度，在50～242 ℃分3步失去结晶水。     

双核单茂钛催化苯乙烯间规聚合反应

二十世纪八十年代,Ishihara等人首次使用钛/甲基铝氧烷(MAO)催化体系成功地制备了间规聚苯乙烯(sPS)[1].此后,由于sPS具有结晶速度快,熔点达270℃,赋予了sPS不同于一般聚苯乙烯的优良性能,因此研制新型的苯乙烯间规聚合催化剂成为国内外的研究热点之一.以往的研究主要集中于催化剂活性的提高,因为单核催化剂只是单一的活性中心,所以只能制备窄分子量分布(MWD)的sPS.近年来,为了提高sPS的加工性能和拓宽sPS的分子量分布,人们使用了不同的茂金属混合物[2,3]或者Z iegler-Natta催化剂的氢化物和单一的茂金属进行了诸多尝试[4,5].至今,…     

Thermodynamic characteristics of thermal dissociation of platinum dichloride

The dissociation pressure for the process PtCl₂(s) → Pt(s) + Cl₂(g) was measured by the static method with diaphragm zero-pressure gauges. The approximating equation for the temperature dependence on the dissociation pressure for the above reaction was found. The enthalpy (137.7±0.3 kJ mol⁻¹) and entropy (163.6±0.4 J mol⁻¹ K⁻¹) of PtCl₂(s) dissociation and enthalpies of formation and absolute entropies of platinum di- and trichlorides at 298.15 K were calculated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1345–1348, June, 2005.     

Sterically hindered active centres in cationic polymerization: Tertiary aromatic amines in the polymerization of 1,3-pentadiene initiated by aluminum trichloride in non-polar solvent

Previous work on the polymerization of 1,3-pentadiene initiated by aluminum trichloride (AlCl₃) in non-polar solvent at 20 °C in the presence of triphenylamine (NPh₃) has highlighted a stabilization of the active centres and a solubilization of AlCl₃ induced by NPh₃ [Delfour M, Bennevault-Celton V, Anh Nguyen H, Cheradame H, Macedo A. Macromol Chem Phys 2004;205:2312-26]. This paper reports the effect of 9-phenylcarbazole, the structure of which is close to that of NPh₃. The results showed a strong decrease of the insoluble fraction (IF), however this electron donor (ED) was a transfer agent alike NPh₃ (alkylation of aromatic rings by the growing polymer chains). To reduce transfer reaction, the influence of two para-substituted triphenylamines—tribromophenylamine (N(PhBr)₃) and tri-p-tolylamine (N(PhCH₃)₃)—on the polymerization of 1,3-pentadiene was studied in the same conditions. Although the presence of Br substituents has no effect on IF, it induced a decrease in the termination reactions with the counter-ion and the transfer reactions. Concerning methyl groups, it has been shown a strong decrease of IF and a negligible amount of alkylation reaction. Moreover the quantity of grafted molecules was reduced and tri-p-tolylamine reduced both the reactions of cyclization and isomerization. Thanks to the stabilization of the active centres by N(PhCH₃)₃ and probably the solubilization of aluminum trichloride, it was possible to obtain a more precisely defined polypentadiene than ever by cationic polymerization in a non-polar medium.     

Thermodynamic characteristics of thermal dissociation of platinum trichloride

Single crystals of platinum trichloride were grown for the first time. The IR spectrum of single-crystal PtCl₃ was recorded. The pressure of thermal dissociation of PtCl₃ was measured by the static method with a quartz membrane-gauge zero-pressure manometer. An approximating equation for the dissociation pressure vs. temperature (540 K ≤ T ≤ 775 K) for the reaction 2 PtCl₃(s) → 2 PtCl₂(s) + Cl₂(g) was found. The enthalpy (123.1±1.7 kJ mol⁻¹) and entropy (183.6±2.8 J mol⁻¹ K⁻¹) for the dissociation of PtCl₃(s) were calculated at 298.15 K.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2032–2034, October, 2004.     

Reactions of pentafluoroaniline with aromatic trihalomethyl derivatives in the presence of AlCl3

The reactions of pentafluoroaniline with aromatic CX₃-derivatives (X = F, Cl) in the presence of AlCl₃ were studied. It was shown that compounds with a CF₃ group can be used in reactions with polyfluoroaromatic amines instead of CCl₃-derivatives for the synthesis of imidoyl chlorides. In the case of compounds with several CX₃ groups, the formation of the imidoyl chloride moiety predominantly involves one of the CX₃ groups under the conditions studied. The introduction of a second CX₃ group can be carried out only under more drastic conditions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1089–1094, June, 1994.