[Co(3,3-tri)(amp)Cl][ZnCl4]一对邻位差向异构体的晶体结构

The crystal structures of a pair isomers of [Co(3,3-tri)(amp)Cl][ZnCl₄] (here 3,3-tri = N-(3-Aminoprop- yl)-1,3-propanediamine; amp=2-(Aminomethyl)pyridine) have been determined by single crystal X-ray diffrac-tion. They are the epimers with the only difference of the orientation of the Sec-NH proton in 3,3-tri ligand. The crystals with the anti-epimer (m1[ZnCl₄]·CH₃OH·H₂O) are monoclinic, space group C2/c with eight molecules in a unit cell of dimensions a=30.401(5)?,b=8.0469(13)?,c=18.817(3)?,β=93.346(3)°,V=4595.3(12)?³,D_c=1.708g·cm^-3,Z=8,F₀₀₀=2416,R=0.0462,R_w=0.1304. The crystals of the syn-epimer (m2[ZnCl₄]·H₂O) are triclinic, space group P1 with two molecules in a unit cell of dimensions a=8.9752(12)?,b=9.8855(12)?,c=12.6886(16)?,α=89.228(3)°,β=76.447(2)°,γ=80.428(3)°,V=1078.8(2)nm³,D_c=1.721g·cm^-3,Z=2,F₀₀₀=568,R=0.0313,R_w=0.0929. The crystal parameters, such as bond lengths and angles, are well consistent with the data of an ab initio computational result (RHF/LANL2DZ opti-mised structure). The average error for bond length is about 1.6%, only two of them in the isomer m3 (Co-N2 and Co-N4) are over 3%, (3.09% and 4.28% respectively). The errormax for bond angle is 2.52%, the bond angles with an over 2% error are only 3.6% out of all bond angles.     

Synthesis of [TpRu(CO)(PPh3)]2(μ-CHCHCHCHC6H4CHCHCHCH) from Wittig reactions

Treatment of [Ru(CHCHCH₂PPh₃)X(CO)(PPh₃)₂]⁺ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh₄ produced [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄. Reaction of RuHCl(CO)(PPh₃)₃ with HCCCH(OEt)₂ produced Ru(CHCHCH(OEt)₂)Cl(CO)(PPh₃)₂, which reacted with KTp to give TpRu(CHCHCHO)(CO)(PPh₃). Treatment of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and benzaldehyde produced TpRu(CHCHCHCHPh)(CO)(PPh₃). The later complex was also produced when TpRu(CHCHCHO)(CO)(PPh₃) was treated with PhCH₂PPh₃Cl/NaN(SiMe₃)₂. The bimetallic complex [TpRu(CO)(PPh₃)]₂(μ-CHCHCHCHC₆H₄CHCHCHCH) was obtained from the reaction of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and terephthaldicarboxaldehyde.     

α′-苯磺酰基-α,β-不饱和酮与开链二烯烃的不对称催化环加成反应

在手性金属钛催化剂存在下 ,研究了α′ 苯磺酰基 α ,β 不饱和酮与开链二烯的不对称催化环加成反应 ,讨论了α′ 苯磺酰基 α ,β 不饱和酮与开链二烯的反应活性和对映选择性 ,以高的收率和光学纯度合成了环己烯衍生物 ,并对部分产物的构型进行了鉴定     

咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.     

Effects of various donor: acceptor blend ratios on photophysical properties in non-fullerene organic bulk heterojunctions

In this work, the donor:acceptor ratio effected photophysical properties of non-fullerene organic solar cells are comparatively investigated. Effective transportation of the photo-generated charge carriers can be obtained with the PDBD-T:ITIC ratio variation. There is no significant energy loss variation exists in the process of changing the D:A ratio.     

Palladium-benzimidazolium salt catalyst systems for Suzuki coupling: development of a practical and highly active palladium catalyst system for coupling of aromatic halides with arylboronic acids

Palladium-benzimidazolium salt catalyst systems have been studied for the Suzuki coupling. A different substitutent effect has been uncovered with respect to nitrogen substituents in the benzimidazolium salts from the palladium-imidazolium salt analogs. A practical and highly active palladium catalyst system, PdCl₂/N,N′-dibenzylbenzimidazolium chloride 2, has been identified for the Suzuki coupling of aromatic halides with arylboronic acids. The coupling of a wide array of aromatic halides with arylboronic acids with the PdCl₂-2 catalyst system gave good to excellent yields. The effective palladium loading could be as low as 0.0001 mol% and 0.01-0.1 mol% for iodide and bromide substrates, respectively. The coupling of unactivated aromatic chlorides with arylboronic acids also gave good results using Cs₂CO₃ as base with a 2 mol% palladium loading. The electronic factors from aromatic halides exert a significant influence on the Suzuki coupling catalyzed by the PdCl₂-2 system while the electronic effect from the arylboronic counterparts is negligible. The aromatic halides with modest steric hindrance could also couple smoothly with phenylboronic acids using the PdCl₂-2 catalyst system.     

Mesoscale organization of CuO nanoribbons: formation of "dandelions"

A two-tiered organizing scheme with multiple-length scales for construction of dandelion-like hollow CuO microspheres has been elucidated: (1) mesoscale formation of rhombic building units from smaller nanoribbons via oriented aggregation and (2) macroscopic organization of these units into the CuO microspheres. This self-assembly concept may also be applicable to other metal oxides by creating geometric constraints for constructional units.     

金复合介孔SBA-15吸附血红蛋白在H2O2电催化反应中的应用

以P123嵌段共聚物表面活性剂为模板剂制备介孔氧化硅SBA-15,并用沉积-沉淀(DP)法在SBA-15介孔表面负载纳米Au颗粒制备得到金复合介孔SBA-15材料(Au-SBA-15).再以Au-SBA-15材料制备玻碳修饰电极,将血红蛋白固定于修饰电极上用循环伏安法考察其对不同浓度H2O2溶液的电催化反应.在固定了血红蛋白的Hb/Au-SBA-15/GC修饰电极上,H2O2在+0.95 V处出现了氧化峰,且随着H2O2浓度的增大峰电流不断增加,说明金复合介孔氧化硅材料具有良好的生物兼容性,有利于血红蛋白的固定,其修饰电极对H2O2溶液具有一定的电催化作用.     

有害杂草的微量元素分析

紫茎泽兰和水葫芦均属有害杂草，大规模防治的有效方法还未找到，本文分析研究了采自昆明郊区的紫茎泽兰和滇池水域的水葫芦中微量元素的含量，为进一步开发利用这两种杂草提供科学依据。     

一步法合成吲哚用Ag／SiO2催化剂的失活及其抑制

 用简单浸渍法制备了Ag／SiO2催化剂．该催化剂对苯胺和乙二醇一步合成吲哚表现出很高的催化活性，但同时存在明显的失活．TG，XRD和TEM表征结果表明，催化剂失活的主要原因是反应过程中催化剂表面的积碳和银粒子的烧结．向反应体系中通入氢和水蒸气能够减少催化 剂表面的积碳；向催化剂体系加入ZnO助剂能较大程度地提高银的分散度，并能有效抑制反应过程中银粒子的烧结．