μ—4,4‘—联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４’－联吡啶为配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ３（４，４＇－ｂｐｙ）３．（ｐｈｅｎ）３］（ＣｌＯ４）６．２Ｈ２Ｏ（１），［Ｃｕ３（４，４＇－ｂｐｙ），（ｂｐｙ）３］（ＣｌＯ４）６．Ｈ２Ｏ（２）和［Ｃｕ３９４，４＇－ｂｐｙ）３．（ＮＯ２－ｐｈｅｎ）３］（ＣｌＯ４）６．６Ｈ２Ｏ（３）。经元素分析，电导，ＩＲ，电子光谱，ＥＳＲ，磁化率等方法进行了表征，推定该配合物具有以４，４’－联吡     

2—溴代对苯二甲酸根桥联双核钴（Ⅱ）配合笺的合成,磁性及抗癌活性

合成了三种以２－溴代对苯二甲酸为桥联配体的新型双核钴（Ⅱ）的配合物，即［Ｃｏ２（ＢＴＰ）（ｐｈｅｎ）４］（ＣｌＯ４）２．Ｈ２Ｏ（配合物１）、［Ｃｏ２（ＢＴＰ）（Ｎｐｈｅｎ）４］（ＣｌＯ４）２．２Ｈ２Ｏ（配合物２）和［Ｃｏ２（ＢＴＰ）（Ｂｐｙ）４］ＣｌＯ４）２，２ＨＯ（配合物３）（ＢＴＰ＝２－溴代对苯二甲酸根，ｐｈｅｎ＝１，１０－菲罗啉，Ｎｐｈｅｎ＝５－硝基－１，１０－菲罗啉，Ｂｐｙ－２，２＇联吡啶     

2-溴代对苯二甲酸根桥联双核钴(Ⅱ)配合物的合成、磁性及抗癌活性

合成了三种以２－溴代对苯二甲酸根为桥联配体的新型双核钴（Ⅱ）的配合物，即［Ｃｏ２（ＢＴＰ）（ｐｈｅｎ）４］（ＣｌＯ４）２·Ｈ２Ｏ（配合物１）、［Ｃｏ２（ＢＴＰ）（Ｎｐｈｅｎ）４］（ＣｌＯ４）２·２Ｈ２Ｏ（配合物２）和［Ｃｏ２（ＢＴＰ）（Ｂｐｙ）４］（ＣｌＯ４）２·２Ｈ２Ｏ（配合物３）（ＢＴＰ＝２－溴代对苯二甲酸根，ｐｈｅｎ＝１，１０－菲罗啉，Ｎｐｈｅｎ＝５－硝基－１，１０－菲罗啉，Ｂｐｙ＝２，２′－联吡啶）。使用元素分析、ＩＲ、ＵＶ－Ｖｉｓ光谱和电导测定方法对该配合物进行了表征。测定了配合物的变温磁化率，并对所得数据进行了理论分析，求得了配合物１、配合物２和配合物３的自旋磁交换积分分别为：２Ｊ＝－６．５ｃｍ－１，２Ｊ＝－７．８ｃｍ－１和２Ｊ＝－８．９ｃｍ－１。对该三配合物进行了体外抗人白血病癌细胞的实验。发现该三配合物均具有一定的抑制癌细胞的活性     

μ－4，4＇－联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４＇－联吡啶为桥联配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·２Ｈ＿２Ｏ（１）、［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３］（ｂｐｙ）＿３］（ＣｌＯ＿４）＿６·Ｈ＿２Ｏ（２）和［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ＮＯ＿２－ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·６Ｈ＿２Ｏ（３）。经元素分析、电导、ＩＲ、电子光谱、ＥＳＲ、磁化率等方法进行了表征，推定该配合物具有以４，４＇－联吡啶为扩展桥的结构。利用Ｈｅｉｓｅｎｂｅｒｇ模型求得交换参数Ｊ值为－０．２３ｃｍ－１（１）和－０．９０ｃｍ－１（３），表明配合物中金属离子间仅有很弱的反铁磁交换作用．     

Yb(Cl_4)_3·3H_2O-18C6-C_2H_5OH体系(25℃)的相化学研究及固态配合物的合成与性质

王冠醚能选择性配位于阳离子,使无机盐溶于有机溶剂及类似酶功能的特性,因而引起人们很大的研究兴趣。文献［１］报道在乙腈中制得了组成为：Ｃｅ（ＣＩＯ４）３·１８Ｃ６的配合物;文献［２］在乙腈中制得了组成为 ＲＥ（ＣＩＯ４） ３· １８Ｃ６（ＲＥ＝ Ｐｒ, Ｅｕｆ）的配合物;而 ＲＥ（ＣＩＯ４） ３·３Ｈ２Ｏ－１８Ｃ６－ＣＨ３ＣＮ体系（ＲＥ＝ Ｄｙ, Ｙ）的相化学研究指出：体系中均形成两种化学计量的配合物［３·４］。Ｙｂ（ＣＩＯ４）３·３Ｈ２Ｏ与１８Ｃ６在乙醇中的配合行为未见报道。为了寻找制备配合物的热力学依…     

3－硝基邻苯二甲酸根桥联双核钴（Ⅱ）配合物的合成、磁性及抗癌活性

合成了两种以３－硝基邻苯二甲酸根为桥联配体的新型双核钴（Ⅱ）的配合物，即［Ｃｏ２（３ＰＴ）（Ｐｈｅｎ）４］·（ＣｌＯ４）２·４Ｈ２Ｏ（配合物１）和［Ｃｏ２（３ＰＴ）（ＮＰｈｅｎ）４］（ＣｌＯ４）２·５Ｈ２Ｏ（配合物２）（３ＰＴ＝３－硝基邻苯二甲酸根，Ｐｈｅｎ＝１，１０－菲口罗啉，ＮＰｈｅｎ＝５－硝基－１，１０－菲口罗啉）。使用元素分析，ＩＲ，ＵＶ－ｖｉｓ和电导测定方法对该两配合物进行了表征。测定了配合物的变温磁化率，并对所得数据进行了理论分析，求得了配合物１、２的磁交换积分均为２Ｊ＝－９．２ｃｍ－１。对配合物进行了体外抗人白血病癌细胞实验。发现该两配合物均具有较强的抑制人白血病癌细胞的活性。     

三元体系Y(ClO4)3·3H2O—B15C5—CH3OH(25℃)的半微量相平衡研究

采用半微量相平衡方法研究了三元体系Ｙ（ＣｌＯ４）３．３Ｈ２Ｏ－Ｂ１５Ｃ５－ＣＨ３ＯＨ在２５℃的溶解度，测定了各饱和溶液的折光率。该体系在２５℃生成三种化学计量的配合物，其组成分别为：４Ｙ（ＣｌＯ４）３．３Ｂ１５Ｃ５．１２Ｈ２Ｏ．１２Ｃｈ３ＯＨ（Ｉ），Ｙ（ＣｌＯ４）３．２Ｂ１２Ｃ５．３Ｈ２Ｏ．Ｃｈ３ＯＨ（Ⅲ），其中配合物（Ｉ）和（Ⅱ）是溶解不一致化合物。在甲醇溶剂中，分离制备了配合物（Ⅲ），在６９－     

As-V-O簇合物对乙苯选择氧化反应的催化活性

通过水热方法合成了簇合物［Ｎ（ＣＨ３）４］４［Ａｓ８Ｖ１４Ｏ４２（８Ｈ２Ｏ）］及其相近的同多及杂多钒氧簇Ｋ６Ｖ１０Ｏ２８·９Ｈ２Ｏ，ＮａＫＶ２Ｏ６，（Ｈ２Ｅｎ）０．５Ｖ２Ｏ５，（Ｈ２Ｅｎ）３（ＶＯ）９（ＰＯ４）８，Ｎａ３ＶＯ（ＨＰＯ４）（ＰＯ４）·Ｈ２Ｏ．运用ＸＲＤ和ＩＲ等手段表征了［Ｎ（ＣＨ３）４］４［Ａｓ８Ｖ１４Ｏ４２（８Ｈ２Ｏ）］的结构．该类化合物对于催化乙苯过氧化氢选择氧化制苯乙酮具有较高的催化活性．通过比较含钒与不含钒化合物的活性情况，讨论了催化氧化的活性中心．     

双核配合物［Cu_2（C_6H_5COO）_4（C_3H_4NS）_2］的合成

双核配合物［Ｃｕ＿２（Ｃ＿６Ｈ＿５ＣＯＯ）＿４（Ｃ＿３Ｈ＿４ＮＳ）＿２］的合成与表征王冬梅，杨瑞娜，胡晓院，侯益民，薛室玉，金斗满（河南化学研究所，郑州４５０００３）关于双核铜（ＩＩ）配合物的合成，曾有不少文献报道￣［１－４］。但这些合成大都是利用铜...     

1，2－亚丙基双（草酰胺根）桥联的线性三核铜（Ⅱ）配合物的合成与磁性

本文合成和表征了四种新的三核铜（Ⅱ）配合物｛［Ｃｕ（Ｌ）］２［Ｃｕ（ＣＨ３－ｅｂｏ）］｝（ＣｌＯ４）２（ＣＨ３ｅｂｏ表示１，２－亚丙基双（草酰胺根），Ｌ表示１，１０－菲咯啉（ｐｈｅｎ）（１），５－硝基－１，１０－菲咯琳（ＮＯ２－ｐｈｅｍ）（２），２，２’－联吡啶（ｂｐｙ）（３）和４，４’－二甲基－２，２’－联吡啶（Ｍｅ２ｐｙ）（４））．测定了四种配合物的变温磁化率（７７－３００Ｋ），求得交换参数分别为Ｊ１＝－２１９．６ｃｍ－１，Ｊ２＝－１９１．７ｃｍ－１，Ｊ３＝－２００．８ｃｍ－１，Ｊ４＝－１８５．５ｃｍ－１，表明Ｃｕ（Ⅱ）－Ｃｕ（Ⅱ）离子间存在着强的反铁磁交换相互作用．     

Improving the Performance of Heterogeneous Borane Cocatalysts by Pretreatment of the Silica Support with Alkylaluminum Compounds

The treatment of silica with alkylaluminum compounds, triisobutylaluminum (TIBA) and triethylaluminum (TEA), dramatically enhanced the cocatalytic performances of the [CPh₃]⁺[B(C₆F₅)₃—SiO₂]^–. We measured the productivity and ethylene‐consumption profiles for [CPh₃]⁺[B(C₆F₅)₃—SiO₂]^– cocatalysts and Cp₂ZrCl₂/TIBA. Both of the treated cocatalyst systems improved the average molecular weight of the product when compared with the untreated cocatalyst system. The TIBA‐treated cocatalyst provided a narrow molecular weight distribution while the TEA‐treated cocatalyst system gave a broad distribution.     

Preparation of syndiotactic polystyrene using the doubly bridged dinuclear titanocenes

As a new kind of dinuclear metallocene four DBDM (doubly bridged dinuclear metallocene) that hold two different bridging units linking two metallocenes have been prepared and their polymerization properties have been pursued. The selected bridging ligands for DBDM were polymethylene and dialkoxy terminated derivatives to bond two cyclopentadienyls and two titanium centers, respectively. The syntheses of new dinuclear metallocenes 5-8 were able to be achieved by the reaction between dinuclear half-titanocenes 1 and 2 and ditrimethylsiloxy terminated derivatives 3 and 4 at −78 °C. The EI mass spectra and ¹H and ¹³C NMR spectral data were very informative to identify their formulations as well as structural features. The polymerization of styrene was conducted by using DBDM 5-8. From the polymerization studies it was found that (i) DBDM 7 and 8 holding 2,2-diethyl-1,3-dipropanoxy (DEP) bridge not only show greater activity but also produce higher syndiotactic polystyrene than DBDM 5 and 6 holding 1,1,4,4-tetramethyl-1,4-dibutanoxy (TMB) bridge between two titanium centers, (ii) activities increase with increase in the polymerization temperature, the amount of cocatalyst and monomer concentration, (iii) the most crucial factor to control the stereoregularity of the resulting polystyrene is the styrene concentration in reaction system, (iv) surprisingly the catalyst structure does not have much effect on molecular weight of the obtained polystyrenes. The most significant feature from this study is that the second bridging dialkoxy terminated ligands connecting two titanium centers likely exert more pronounced influence than the polymethylene bridges between two Cp groups on the activity of the catalyst as well as the stereochemistry of the generated polymers.     

取代戊二烯Ti,V羰基化合物的谱学研究

利用IR，EPR和UV-VIS方法对系列取代戊二烯基钛，钒羰基化合物进行了表征，用EHMO方法对开环夹心化合物[2,4-(CH_3)_2C_2H_5]_2VCO和开、闭环夹心化合物[2,4(CH_3)_2C_5H_5](C_5H)5)VCO进行了计算，对开环夹心羰基化合物，开、闭环夹心羰基化合物及闭环夹心羰基化合物进行了比较．结果表明，开、闭环夹心羰基化合物的性质介于开环夹心羰基化合物和闭环夹心羰基化合物之间，且更接近于开环夹心羰基化合物，开环配体与Ti，V间的化学键较强，对于化合物性质影响较大．     

夹心化合物［C_5HMe_4］_2TiCl_2的合成及谱学表征

用四甲基环戊二烯基［Ｃ_５ＨＭｅ_４］~－为配体合成了夹心化合物［Ｃ_５ＨＭｅ_４］_２ＴｉＣｌ_２，通过核磁共振、质谱、红外光谱、拉曼光谱等多种谱学方法对该化合物进行了结构表征，实验结果表明［Ｃ_５ＨＭｅ_４］_２ＴｉＣｌ_２中两个［Ｃ_５ＨＭｅ_４］~－配体对称分布在Ｔｉ（Ⅳ）两侧，整个分子具有Ｃ_２ｖ对称性，呈覆盖型结构。     

Dialkylzinc Compounds as Chain Transfer Agents in Ethylene and Propylene Polymerizations Catalyzed by Metallocene Catalysts

Dialkylzinc compounds (ZnR₂) with the alkyl groups of different steric hindrance were used as chain transfer agents in ethylene and propylene polymerizations catalyzed by two conventional metallocene catalysts including rac-Et(Ind)₂ZrCl₂ and rac-Me₂Si[2-Me-4-Ph-Ind]₂ZrCl₂. In general, catalyst activities for ethylene polymerizations are barely affected by chain transfer agents, regardless of the R type; however, there are significant activity reductions in propylene polymerizations when the R in ZnR₂ is less hindered, and as R becomes bulkier, catalyst activities are gradually restored. ZnR₂ and metallocene catalyst active site tend to form a reversible and catalytically inactive complex, thus the geometry congested ZnR₂ would reduce complex formation tendency and hence decreased its negative effect on catalyst activities.     

Effects of low hydrogen partial pressures on propylene polymerization by Cp*TiMe2(μ-Me)B(C6F5)3

Polymerization of propylene by Cp*TiMe₂(μ-Me)B(C₆F₅)₃ in the presence of increasing partial pressures of H₂ results in ever decreasing polymer molecular weights, which is consistent with the hydrogenolytic chain transfer processes involving metal–polymer bonds in many heterogeneous and homogeneous systems. However, catalytic activities are not significantly increased as the extent of hydrogenolysis increases, unlike metallocene catalyst systems in which the H₂ reacts primarily with dormant catalytic sites containing propylene 2,1-insertion products. It was shown previously that monocyclopentadienyl systems do not become seriously deactivated following 2,1 insertions, and thus hydrogenolysis does not result in enhanced activities. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4386–4389, 1999     

Metallocene supported on a polyhedral oligomeric silsesquioxane‐modified silica with high catalytic activity for ethylene polymerization

A polyhedral oligomeric silsesquioxane (POSS) consisting of a mixture of perfect and imperfect polyhedra with 8–10 Si atoms bonded to bulky and branched organic groups functionalized with (β‐hydroxy)‐tertiary amines, was adsorbed on an activated silica from a toluene solution. POSS fixation was confirmed by measuring its concentration in the solutions resulting from filtering and repeatedly washing with toluene. Diffuse reflectance infrared Fourier‐transformed (DRIFTS) spectra of the modified silica showed a decrease in the absorption of isolated SiOH groups. A POSS previously marked by reaction with an isocyanate was also used, and the presence of the carbonyl in the urethane group was recorded in the DRIFTS spectra of the modified silica, confirming the presence of adsorbed POSS. X‐ray photoelectron spectroscopy (XPS) was used to measure the amount of Si (2p) of POSS adsorbed on the SiO₂ surface as a function of the POSS concentration in the toluene solution. A linear increase of adsorbed POSS as a function of its concentration in toluene was found, even after successive washings with toluene. A metallocene, (nBuCp)₂ZrCl₂, was then adsorbed on the POSS‐modified silica from a toluene solution, and the fixed Zr amount was measured by Rutherford backscattering spectrometry (RBS). The activity of the resulting catalyst for ethylene polymerization in toluene, using methylaluminoxane (MAO) as a cocatalyst, was determined in two different devices operating in the range of 1.6–7.0 bar. Under every experimental condition, POSS‐modification of the silica support led to an increase of about 50% in the activity of the resulting catalyst when compared to the use of the unmodified support. Reasons for the observed increase in activity are discussed. The molar mass distribution and crystallinity of the resulting polyethylenes was not affected by the POSS modification of the silica support. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5465–5476, 2005     

Ethylene/1‐hexene copolymerization with tetramethyldisiloxane‐bridged bis(indenyl) metallocenes

Ethylene/1‐hexene copolymerizations with disiloxane‐bridged metallocenes, rac‐ and meso‐1,1,3,3‐tetramethyldisiloxanediyl‐bis(1‐indenyl)zirconium dichloride (rac‐ 1 , meso‐ 1 ) activated by modified methylaluminoxane were performed to investigate the influence of conformational dynamics on comonomer selectivity. Although ¹H NOESY (nuclear Overhauser and exchange spectroscopy) analysis indicated that the most stable conformation for the meso isomer in solution was that in which both indenes project over the metal coordination site, this isomer showed higher 1‐hexene selectivity in copolymerization (r_e = 140 ± 30, r_h = 0.024 ± 0.004) than the rac isomer with only one indene over the coordination site (r_e = 240 ± 20, r_h = 0.005 ± 0.001). The meso isomer showed high 1‐hexene selectivity, a high product of reactivity ratios (r_er_h = 3.3 ± 0.5) and produced copolymers that could be separated into fractions with different ethylene content suggesting that the active species exhibited multisite behavior and populated conformations with different comonomer selectivities during the copolymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3323–3331, 2004     

Unconstrained geometry complexes: Ethylene/α‐olefin copolymerizations with a tetramethyldisilyl‐bridged Cp‐amido titanium complex

A new disilyl‐bridged complex, [(N‐tert‐butylamido)(3‐indenyl)tetramethyldisilyl]titanium dichloride ( 3 ), was synthesized and activated with methylaluminoxane (MAO) for propylene homopolymerization and ethylene/propylene and ethylene/1‐hexene copolymerizations. A polypropylene with a slight isotactic enrichment was obtained. The number of regioerrors present in the polypropylene was somewhat smaller than that found in most polypropylenes made from monosilyl‐bridged [(N‐tert‐butylamido)(3‐indenyl)dimethylsilyl]titanium dichloride. The regioerrors detected in the copolymers obtained from 3 /MAO were on the order of the amounts observed in polymers made with the monosilyl‐bridged constrained geometry catalysts. Ethylene copolymers of propylene and 1‐hexene had random sequence distributions and showed significant comonomer incorporation. Because of the presence of regioerrors, a modified method for determining the monomer composition and sequence distribution was developed from the direct measurement of the monomer content from the number of methylene and methine carbons per polymer chain, regardless of propylene inversion. An estimate of the error in the copolymerization reactivity ratio determination for regioirregular ethylene/α‐olefin copolymers was obtained by the calculation of the reactivity ratios from monomer dyad sequences, with consideration given to the contribution of major regioirregular sequences. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3840–3851, 2005