不同激发波长下ZnPcSP的光敏化能力和抗癌活性

研究了激发光的波长对金属酞菁配合物ＺｎＰｃＳＰ光敏化产生Ｏ２的能力和光动力癌作用的影响，结果表明，激发波长对ＺｎＰｃＳＰ配合物光敏化产生Ｏ２的能力和光动力抗癌作用的影响显示了同样的规律性，波长为６７０ｎｍ的光具有较佳的激发效率，研究结果同时说明ＺｎＰｃＳＰ在光动力治癌中的主要光敏反应机制可能是产生Ｏ２的Ⅱ型反应机制。     

Catalysts for cross-coupling reactions with non-activated alkyl halides

Despite the problems inherent to metal-catalyzed cross-coupling reactions with alkyl halides, these reactions have become increasingly important during the last few years. Detailed mechanistic investigations have led to a variety of novel procedures for the selective cross-coupling of non-activated alkyl halides bearing beta hydrogen atoms with a variety of organometallic nucleophiles under mild reaction conditions. This Minireview highlights selected examples of metal-catalyzed coupling methods and is intended to encourage chemists to exploit the potential of these approaches in organic synthesis.     

微波辐照引发甲烷部分氧化制合成气 Ⅱ.Ni/La2O3,Ni/ZrO2,Co/La2O3和Co/ZrO2的催化性能

甲烷部分氧化(POM)制合成气所用的催化剂主要是负载型Rh、Ni等过渡金属催化剂和复合(或混合)氧化物催化剂等[1～9].其中以活性组分Rh的催化活性最佳,稳定性也最好.但由于Rh的价格昂贵,因而其应用受到限制.Chen等[3]曾比较了第一系列过渡金属催化剂的催化活性,结果发现,只有Ni和Co对POM反应具有较高的活性和选择性.     

Linear functionalized polyethylene prepared with highly active neutral Ni(II) complexes

Neutral Ni(II) salicylaldimine catalysts (pendant ligand = NCMe or PPh₃) were used to copolymerize ethylene with monomers containing esters, alcohols, anhydrides, and amides and yielded linear functionalized polyethylene in a single step. α‐Olefins and polycyclic olefin comonomers carrying functionality were directly incorporated into the polyethylene backbone by the catalysts without any cocatalyst, catalyst initiator, or other disturber compounds. The degree of comonomer incorporation was related to the monomer structure: tricyclononenes > norbornenes > α‐olefins. A wide range of comonomer incorporation, up to 30 mol %, was achieved while a linear polyethylene structure was maintained under mild conditions (40 °C, 100 psi ethylene). Results from the characterization of the copolymers by solution and solid‐state NMR techniques, thermal analysis, and molecular weight demonstrated that the materials contained a relatively pure microstructure for a functionalized polyethylene that was prepared in one step with no catalyst additive. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2842–2854, 2002     

Synthesis, structures, and magnetic properties of binuclear carboxylate complexes with NiII and NiIII atoms

The reaction of NiCl₂·6H₂O with Me₃CCOOH and KOH taken in a molar ratio of 1:2:2 in water afforded the nonanuclear antiferromagnetic complex Py₂Ni₂(Me₃CCOOH)₂(OOCCMe₃)₂(μ-OOCCMe₃)₂(μ-OH₂), which apparently contains Ni^II and Ni^III atoms. The complex was isolated by extraction with CH₂Cl₂, benzene, or hexane. The reactions of this complex with pyridine bases (pyridine (Py), 3,4-lutidine (Lut), and nicorandil (Nic)) gave the adducts L₄Ni₂(OOCCMe₃)₂(μ-OOCCMe₃)₂(μ-OH) (L=Py, Lut, or Nic, respectively). According to magnetic measurements, intramolecular ferromagnetic exchange interactions in these adducts are complemented by intermolecular antiferromagnetic interactions. Pyrolysis of the pyridine adduct in air or under an inert atmosphere in xylene yielded the antiferromagnetic complex Py₂Ni₂(Me₃CCOOH)₂(OOCCMe₃)₂(μ-OOCCMe₃)₂(μ-OH₂), which contains Ni^II atoms. The structures of all the complexes synthesized were established by X-ray diffraction analysis. The electronic absorption spectra of these compounds are considered. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 725–738, April, 1998.     

具有平面结构的四齿肼基硫代甲酸苄酯席夫碱镍配合物的合成,晶体结构和三阶非线性光学性质研究

０IntroductionThereiscurrentlyintenseresearchinterestinde－velopingnewnonlinearmaterialswithhighthird－ordernonlinearopticaleffectsduetotheirpotentialapplica－tionsinanumberofimportanttechnologiesincludingopticalpowerlimitingforsensorprotection，opticalswitches，allopticalsignalprocessingandopticalcom－puting犤１～３犦．Metalcomplexeswithplanar，π－conjugatedtetradentateorbidentateligandareofparticularinterestbecausetheycontainbothelectronsthatarefreetomovewithintheπextendedsystemoftheligand…     

助剂对甲烷部分氧化制合成气镍基催化剂性能的影响

考察了添加助剂铈、镧和钙对镍基催化剂反应性能的影响，发现助剂对以α-Al2O3为载体的镍基催化剂的调变作用比以γ-Al2O3为载体的镍基催化剂好，且助剂铈对催化剂的性能改善最好。在此基础上，研究了不同载量的铈对催化剂性能的影响。结果表明，铈的质量分数为1%时对催化剂的性能改善最好。同时采用XRD、XPS、TG等技术，研究了助剂铈对10％Ni/γ-Al2O3催化剂的改性作用。XRD分析表明，铈负载量较低时，催化剂中的CeO2高度分散在催化剂表面，铈负载量较高时，CeO2形成微晶颗粒，降低了催化活性。     

Recent progress in tartaric acid‐modified Raney nickel system for enantio‐differentiating hydrogenation

Tartaric acidmodified Raney nickel (TAMRNi) is an enantiodifferentiating catalyst for hydrogenation of ketones. The stereochemical models explaining the enantiodifferentiation of ketoester and 2alkanone were unified as an extended stereochemical model by the experimental supports. Based on this new model, a working hypothesis to improve the enantiomeric excess (ee) of the ketoester/TAMRNi system was developed, and the ee was improved to 96%. By further fine tuning of this system, almost perfect enantiodifferentiation resulting in over 98% ee was achieved.     

[Ni(NH_2NHCO_2CH_3)_3](NO_3)_2·H_2O的制备、晶体结构和热分解机理

由硝酸镍水溶液和肼基甲酸甲酯 (NH2 NHCOOCH3 ,MCZ)的水溶液反应 ,制备出未见文献报道的配合物 [Ni(MCZ) 3 ] (NO3 ) 2 ·H2 O .晶体结构测定结果表明 ,该晶体属单斜晶系 ,P2 1/n空间群 ,晶体学参数为 :a =1.3 681(2 )nm ,b =0 .8188(1)nm ,c =1.60 2 9(4 )nm ,β =92 .16(2 )° ,V =1.7943 (6)nm3 ,Dc=1.744g·cm-3 ,Z =4,F(0 0 0 ) =976,μ(MoKα) =1.166mm-1.结构采用全矩阵最小二乘法优化 ,除氢原子采用各向同性热参数外 ,其它非氢原子均采用各向异性热参数修正 ,最终偏离因子R1=0 .0 3 3 7,wR2 =0 .0 85 7.在该配合物分子中 ,肼基甲酸甲酯作为双齿配体 ,由羰基氧原子和端基氮原子与Ni2 + 配位 ,形成五元平面螯合环 ,配合物分子中共有三个这样的螯合环 ,中心离子为六配位八面体构型 .配合物的外界是两个硝酸根离子和一个水分子 ,通过库仑力和氢键与内界结合在一起 .采用TG DTG ,DSC ,IR等表征了标题化合物的热稳定性 .在程序升温条件下 ,该配合物的热分解过程是由一个弱的吸热过程和三个较强的连续的放热过程组成的 ,由TG DTG和IR分析结果证明 ,在 3 2 5℃时的最终分解产物为NiO ,得到了化合物的热分解机理 .     

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [Cp*Ru(Me2S-C2B9H10)RuCp*]+

The structures of the metallacarborane cations [(-9-Me₂S-7,8-C₂B₉H₁₀)Ni(-Cp)Ni(-9-Me₂S-7,8-C₂B₉H₁₀)]⁺ (2) and [Cp*Ru(Me₂S-C₂B₉H₁₀)RuCp*]⁺ (4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004.