6，6－二烷基富烯与苄基钠的反应研究──取代茂钛、锆化合物的合成

苄基钠与６，６－二烷基富烯及６，６－ｎ亚甲基富烯（ｎ＝４，５，６）皆发生富烯环外双键的加成反应。产生的取代环戊二烯基负离子与ＴｉＣｌ_４、ＺｒＣｌ_４及（ＣｐＴｉＣｌ_２）_２Ｏ络合，合成出２２种新的含或不含手性碳取代茂钛、锆化合物。讨论了反应机理及~１ＨＮＭＲ谱。     

TiCl_4／SiO_2－MgCl_2载体催化剂下的乙烯／己烯－1共聚反应

ＴｉＣｌ_４／ＳｉＯ_２－ＭｇＣｌ_２载体催化剂下的乙烯／己烯－１共聚反应陈辉，张学全，黄葆同王展望，杨永然（中国科学院长春应用化学研究所长春１３００２２）（辽阳化纤公司化工三厂辽阳）关键词乙烯，己烯，共聚，Ｚｉｅｇｌｅｒ－Ｎａｔｔａ催化剂乙烯／α－烯?..     

Grignard试剂同6，6－二烷基富烯反应的研究

烯丙基卤化镁和环戊二烯基溴化镁同６，６－二烷基富烯分别进行富烯环外双键的加成和还原反应，生成的取代环戊二烯基负离子用（ＣｐＴｉＣｌ＿２）＿２Ｏ（Ｃｐ＝环戊二烯基）或ＴｉＣｌ４配合，合成通式为Ｃｐ（Ｃ＿５Ｈ＿１－ＣＲＲ￣１－ＣＨ＿２ＣＨ＝ＣＨ＿２）ＴｉＣｌ＿２和（Ｃ＿５Ｈ＿４ＣＨＲＲ￣１）＿２ＴｉＣｌ＿２的化合物。对烯丙基卤化镁、环戊二烯基溴化镁同富烯的反应机理进行了探讨。     

Cp2ZrCl2—i—BuMgBr催化体系中烯烃的还原二聚

在Ｃｐ２ＺｒＣｌ２－ｉ－ＢｕＭｇＢｒ络合催化体系中研究了烯烃，如１－己烯、１－辛烯、２－辛烯、烯丙基苯、环己烯、苯乙烯等的还原二聚反应，并对其反应机理进行了讨论。     

LaCl_3－SrCl_2－MgCl_2三元体系相图

本文借助于ＤＴＡ和Ｘ射线结构分析测定了ＬａＣｌ_３－ＳｒＣｌ_２－ＭｇＣｌ_２三元体系相图，发现它属简单低共熔型，体系内有对应于ＬａＣｌ_３、ＳｒＣｌ_２和ＭｇＣｌ_２的３个液相面、３条２次结晶线和１个三元低共熔点Ｅ（１５．０ｗｔ％ＬａＣｌ_３，４９．５ｗｔ％ＳｒＣｌ_２，３５．５ｗｔ％ＭｇＣｌ_２；５４５℃），并且在固相下有一个不稳定的化合物生成，在约５００℃时分解。     

Crystal and Molecular Structure of a New Mono－substituted Titanocene Complex，｛（η~5－Cp）［η~5－（1－（4－OCH_3）C_6H_4）C_6H_（10）Cp］（TiCl_2）｝·0．3（n－C_6H_（14））

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆａＮｅｗＭｏｎｏ－ｓｕｂｓｔｉｔｕｔｅｄＴｉｔａｎｏｃｅｎｅＣｏｍｐｌｅｘ，｛（η~５－Ｃｐ）［η~５－（１－（４－ＯＣＨ_３）Ｃ_６Ｈ_４）Ｃ_６Ｈ_（１０）Ｃｐ］（ＴｉＣｌ_２）｝·０．３（ｎ－...     

α-芳硒基羰基化合物的合成

茂钛硒化物分别与α－溴代酮和α－溴代酯反应生产了相应的α－硒酮和α－硒代酯，茂钛硒配合物由Ｃｐ２ＴｉＣｌ２／２ｉ－ＢｕＭｇＢｒ／ＴＨＦ体系还原二芳基二硒醚得到。     

Grignard试剂同6,6—二烷基富烯反应的研究

烯丙基卤化镁和环戊二烯基溴化镁同６，６－二烷基富烯分别进行富烯环外双键的加成和还原反庆，生成的取代环戊二烯基负离子用（ＣｐＴｉＣｌ２）２Ｏ（Ｃｐ＝环戊二烯基）或ＴｉＣｌ４配合，合成式为Ｃｐ（Ｃ６Ｈ４－ＣＲＲ＾１－ＣＨ２Ｃｈ－ＣＨ２）ＴｉＣｌ２和（Ｃ６Ｈ４ＣＨＲＲ＾１）２ＴｉＣｌ２的化合物，对烯丙基卤化镁、环戊二烯基溴化镁同富烯的反应机理进行了探讨。     

茂金属催化剂催化苯乙烯间规聚合 Ⅰ.Cp Ti(CH_2SiMe_3)_3/B(C_6F_5)_3催化体系

考察了新型催化剂Ｃｐ＊Ｔｉ（ＣＨ２ＳｉＭｅ３）３／Ｂ（Ｃ６Ｆ５）３催化苯乙烯间规聚合的性能．结果表明，Ｃｐ＊Ｔｉ（ＣＨ２ＳｉＭｅ３）３与Ｂ（Ｃ６Ｆ５）３等摩尔混合可形成高活性的催化剂，催化活性高达（０．７～１．３７）×１０７ｇ／（ｍｏｌ２·ｈ），聚苯乙烯的间规度为９５％以上．Ｂ（Ｃ６Ｆ５）３／Ｔｉ摩尔比不等于１时，其催化活性和间规立构选择性都明显降低．Ａｌ（ｉ－Ｂｕ）３的加入不仅显著提高催化活性和间规立构选择性，而且还提高了间规聚苯乙烯的相对分子量．最佳聚合温度为３４３Ｋ．在ｃ（Ｓｔ）＝０．４４～６．５６ｍｏｌ／Ｌ范围内，苯乙烯聚合速率对苯乙烯单体呈一级反应，苯乙烯转化率和间规聚苯乙烯的相对分子量随反应时间的增加而提高．     

Ind2rCln（OC6H3—3,5—me2）2—n／二氯二乙基铝催化乙烯齐聚的研究

合成了Ｉｎｄ２Ｚｒ（ＯＣ６Ｈ３－３,５－Ｍｅ）２（Ａ）、Ｉｎｄ２ＺｒＣｌ（ＯＣｙＨ３－３,５－Ｍｅ２）（Ｂ）和Ｉｎｄ２ＡｒＣｌ２（Ｃ）３个化合物,并在不同反应温度、陈化温度、反应时间等条件下,分别考察了每个化合物与Ｅｔ２ＡＩＣｌ所组成的催化体系对乙烯剂聚活笥和选择性的影响。在相同条件下,催化剂活性顺序为Ａ〉Ｂ〉Ｃ,在最佳反应条件下,Ｉｎｄ２Ｚｒ（ＯＣ６Ｈ３－３,５Ｍｅ２）２的催化活必来１９５１ｇ齐     

茂钛类络合物催化碳酸二甲酯和苯酚酯交换反应合成碳酸二苯酯的研究

首次将二氯二茂钛用于碳酸二甲酯和苯酚酯交换合成碳酸二苯酯的反应, 发现二氯二茂钛对该反应来讲是一种性能优良的催化剂; 和钛酸酯类催化剂相比, 茂钛类催化剂在空气中更稳定, 从而更适合于工业化应用. 同时探讨了不同种类茂钛类化合物的催化性能, 发现位阻效应、环戊二烯环的电子分散效应以及取代基的吸电子效应等, 都会影响中心钛原子的Lewis酸性以及相应的催化活性. 总体来讲, 位阻效应越小、环戊二烯环的电子分散效应越大、与中心钛原子连接的取代基的吸电子能力越强, 越有利于反应的进行.     

Characteristics of Titanocene Catalyst Supported on Palygorskite for Ethylene Polymerization

Due to the technical problems observed for homogeneous metallocene catalysts, such as reactor fouling and requirement for large amount of expensive methylaluminoxane (MAO) as cocatalyst, the development of supported metallocene catalysts is very important…     

Hydrogenation of Olefins Catalyzed by Highly Active Titanocene/NaH or n-BuLi Catalyst Systems

IntroductionTitanium metallocenes have been widelystudied as the catalysts for the hydrogenation ofunsaturated hydrocarbons[1— 13 ] .In 1 963,Sloan etal.[1] reported that alkoxyltitanium compounds orCp2 Ti Cl2 with trialkylaluminium acted as goodcatalysts for the hydrogenation of olefins.Then,many active catalystsystems have been developed.The anchoring of titanocene species on supportsyields even more active and more stablehydrogenation catalysts[12 ,13 ] .Various reductives,such as Li Al…     

络合型催化剂丙烯聚合动力学研究

本工作对络合型(Solvay型)TiCl_3催化剂—(C_2H_5)_2AlCl体系丙烯聚合进行了活性中心浓度C_p、链增长速率常数k_p和链增长活化能E_p等的测定,并与常规TiCl_3·0.33AlCl_3进行了比较,C_p以动力学方法求取,数均分子量以粘度法测定经分子量分布校正,结果表明,络合型催化剂活性比常规催化剂高,不仅是由于C_p增高,在更大程度上是由于k_p提高。     

Revelation of the nature of the reducing species in titanocene halide-promoted reductions

The fundamental nature of Ti(III) complexes generated in tetrahydrofuran by reduction of Cp(2)TiCl(2) has been clarified by means of cyclic voltammetry and kinetic measurements. While the electrochemical reduction of Cp(2)TiCl(2) leads to the formation of Cp(2)TiCl(2)(-), the use of metals such as Zn, Al, or Mn as reductants affords Cp(2)TiCl and (Cp(2)TiCl)(2) in a mixture having a dimerization equilibrium constant of 3 x 10(3) M(-)(1), independent of the metal used. Thus, we find it unlikely that the trinuclear complexes or ionic clusters known from the solid phase should be present in solution as previously suggested. The standard potentials determined for the redox couples Cp(2)TiCl(2)/Cp(2)TiCl(2)(-), (Cp(2)TiCl)(2)(+)/(Cp(2)TiCl)(2), Cp(2)TiCl(+)/Cp(2)TiCl, and Cp(2)Ti(2+)/Cp(2)Ti(+) increase in the order listed. However, the reactivity of the different Ti(III) complexes is assessed as (Cp(2)TiCl)(2) greater, similar Cp(2)TiCl approximately Cp(2)Ti(+) > Cp(2)TiCl(2)(-) in their reactions with benzyl chloride and benzaldehyde. None of the reactions proceed by an outer-sphere electron transfer pathway, and clearly the inner-sphere character is much higher in the case of Cp(2)Ti(+) than for (Cp(2)TiCl)(2), Cp(2)TiCl, and in particular Cp(2)TiCl(2)(-). As to the electron acceptor, the inner-sphere character increases, going from benzyl chloride to benzaldehyde, and it is suggested that the chlorine atom in benzyl chloride and the oxygen atom in benzaldehyde may function as bridges between the reactants in the transition state.     

Coordination chemistry of stable radicals: homolysis of a titanium-oxygen bond

Thermolysis of Cp2TiCl(TEMPO) (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) at 60 degrees C in a benzene/CCl4 mixture generates Cp2TiCl2. Kinetic studies implicate a mechanism involving the reversible cleavage of a Ti-O bond to generate the TEMPO radical and Cp2TiCl, which is trapped by CCl4 to give Cp2TiCl2. The rate of this reaction is strongly inhibited by added TEMPO and increases with increasing CCl4 concentration, indicating that the coupling of TEMPO to Cp2TiCl is faster than chloride atom abstraction from CCl4.     

Preparation and characterization of some structural variants of Cp*Ti(1,2-propandiolato) complexes

1,2-Propandiol reacts with Cp*Ti(CH₃)₃ by rapid liberation of methane to yield a dimetallic complex 6 of the net composition (Cp*Ti)₂(1,2-propandiolato)₃. The X-ray crystal structure analysis revealed an unsymmetrical bridging between the [Cp*Ti(1,2-propandiolato)] and [Cp*Ti(1,2-propandiolato)₂] subunits. Cp*TiCl₃ reacts with 1,2-propandiol in a 1:1 stoichiometry in the presence of excess pyridine by replacement of two chlorides by a 1,2-propandiolato ligand. The resulting product was isolated as a dimer 8 and characterized by X-ray diffraction. It exhibits a central Ti₂O₂ ring that was formed by bridging between the two [Cp*TiCl(1,2-propandiolato)] subunits using the oxygen atoms of the primary end of the ligand. From the reaction mixture a more complicated condensation product 9 was isolated in a small yield that contains two [Cp*TiCl(1,2-propandiolato)] units connected in a similar way by a Cp*-free [Ti(1,2-propandiolato)₂] moiety as revealed by its X-ray crystal structure analysis. Complex [Cp*TiCl(1,2-propandiolato)]₂ (8) gives an active catalyst for the syndiotactic polymerization of styrene upon treatment with excess methylalumoxane in toluene solution.     

Titanocene(III) chloride mediated radical induced allylation of aldimines: formal synthesis of C-linked 4'-deoxy aza-disaccharide

Titanocene(III) chloride (Cp(2)TiCl) mediated radical induced allylation of aldimines for the preparation of homoallyl amines is described. The radical was generated from the allyl bromide using Cp(2)TiCl as the radical source. Formal synthesis of C(4)-C(5')-linked 4'-deoxy aza-disaccharide is demonstrated and a study toward the bicyclic skeleton of alkaloids was also accomplished. The radical initiator Cp(2)TiCl was prepared in situ from commercially available titanocene dichloride (Cp(2)TiCl(2)) and Zn dust in THF under argon.     

Synthesis and Anti-inflammatory Action of(η-C5H5)2Ti(Sal)2 and (η-C5H5)2Ti(Clo)2

Two new complexes (Cp)2Ti(Sal)2 and(Cp)2Ti(Clo)2(Cp=Cyclopentadienyl η5-C5H5), have been synthesized in anhydrous THF by the reaction of Hsal(o-hydroxybenzoic acid, salicylate acid) or Hclo[N-(m-chloro-phe-nyl) anthranili acid, acidum clofenamicum] with (Cp)2TiCl2 and characterized by means of elemental analyses, IR, 1H NMR, 13C NMR, UV and molar conductivity. In complex (Cp)2Ti(Sal)2 or (Cp)2Ti(Clo)2, the oxygen atom of the carboxyl group coordinates to Ti(IV) in a monodentate manner. The inhibitory action of the complexes on mouse ear tumefaction caused by croton oil and rat foot granulation growth caused by cotton balls is higher than that of the corresponding ligands Hsal, Hclo and [(Cp)2TiCl2], whereas their toxicity is lower than those of the free ligands.     

Radical promoted Wagner-Meerwein-type rearrangement of epoxides in camphoric systems using a Ti(III) radical source

[Chemical reaction: see text] A radical based Wagner-Meerwein-type rearrangement has been observed in camphoric systems. The radical was generated from the epoxide using Cp2TiCl as the radical source. The radical initiator Cp2TiCl was prepared in situ from commercially available Cp2TiCl2 and Zn dust in THF under argon.