二维网状Cu(ntp)2(H2O)4晶体的直接合成、晶体结构和热分解机理研究

用直接法合成了配合物Cu(ntp)₂(H₂O)₄，并测定了其晶体结构。分子式为C₁₆H₁₆CuN₂O₁₆。晶体属单斜晶系，C2/c空间群，晶胞参数为a=2.266 5(7) nm, b=0.706 8(2) nm, c=1.575 5(4) nm, β=126.42(1)°。对晶体进行了DSC和TG-DTG热分析，根据结果提出了可能的热分解过程。     

[K(HTNR)(H_2O)]_n的制备、晶体结构和热分解机理

通过2，4，6－三硝基间苯二酚（斯蒂芬酸，TNR）与氢氧化钾在乙醇溶液中反 应，首次合成出配位聚合物[K(HINR)-(H_2O)]_n，并测定了其晶体结构。该晶体属 单斜晶系, P2_1/c空间群；晶胞参数： a = 0.7888(1)nm, b = 1.38002(2) nm, c = 0.9520(1) nm, β=8.91(1)°；V = 1.0238(2) nm~3; D_c = 1.954 g/cm~3; Z = 4; F(000) = 608; μ(MoKα) = 0.575 mm~(-1)。用DSC，TG－DTG及FT－IR 等分析方法研究了该配位聚合物的热分解机理。在线性升温条件下，该配合物的热 分解包含两个重叠的弱吸热过程和两个强放热分解过程。分解残渣的红外分析表明 ，在271.9 ℃时，分解残渣中有KNCO与羧酸钾，357.1 ℃时，残渣中只有KNC存在 。     

三元混配配合物[Ni(PMBP-sal)(py)]的合成、表征与晶体结构

合成了混配配合物[Ni(PMBP-sal)(py)]，(PMBP：1-苯基-3-甲基-4-苯亚甲基吡唑啉酮-5，sal：水杨酰肼，py：吡啶)，并用元素分析，IR光谱，紫外可见吸收光谱，循环伏安和单晶X-射线衍射进行表征。结构分析表明N-(1-苯基-3-甲基-4-苯亚甲基吡唑啉酮-5)-水杨酰肼和吡啶与Ni(Ⅱ)配位形成略微畸变的平面正方形化合物。     

Cp*MCpMoFe(CO)7(μ3-S), Cp*MoCpMFe(CO)7(μ3-S) (M = W,Mo) and Cp*WCp*MoFe(CO)7(μ3-S). Crystal structure of CpMoCp*WFe(CO)7(μ3-S)

CpMoFeCo(CO)₇(₃-S) reacts with Cp^*M(CO)₃Cl or CpM(CO)₃Cl (M=W, Mo) to gave the mixed-metal clusters Cp^*WCpMoFe(CO)₇(₃-S) (1), Cp^*MoCpMoFe(CO)₇(₃-S) (2), CpWCp^*MoFe(CO)₇(₃-S) (3), CpMoCp^*MoFe(CO)₇(₃-S) (4) and Cp^*WCp^*MoFe(CO)₇(₃-S) (5). The title clusters have been characterized by i.r., ¹H/¹³C-n.m.r. spectroscopy and their compositions have been confirmed by elemental analyses. The X-ray crystal structure analysis shows the two independent enantiomeric molecules of clusters (1) in one crystal structure unit.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

Evaluation of chiral oxazolines for the highly enantioselective diethylzinc addition to N-(diphenylphosphinoyl) imines

On the basis of the principle that the incorporation of the structurally rigid and conformationally restricted skeleton in beta-amino alcohols is beneficial to the enantioselective diethylzinc addition to imines, a series of chiral oxazolines, which had been designed and conveniently prepared from commercially available (1S,2S)-2-amino-1-phenylpropane-1,3-diol, were applied in the diethylzinc addition to diphenylphosphinoyl imines to give high yields of 68-84% and excellent ee values of 90-95%. The configuration of the product was controlled by the chirality of the carbon bonded to the hydroxyl group in the oxazoline. Oxazolines bearing a para- or meta-substituted phenyl group generally offered higher enantioselectivity than those containing an ortho-substituted phenyl. The X-ray structures of 4f and 4j, in combination with the proposed transition state, preliminarily explained why oxazolines with a para- or meta-substituent on the phenyl group gave higher enantioselectivities than those bearing an ortho-substituent. This successful example using chiral oxazolines to promote the titled reaction implies that a large family of chiral compounds containing an oxazoline ring moiety have the potential to be developed for promoting the highly enantioselective dialkylzinc addition to N-(diphenylphosphinoyl) imines.     

N,N''-苄基-1,2二胺合铜的合成和晶体结构及与DNA的相互作用

A ligand, (N,N'-dibenzylethane-1,2-diamine) (L), and its complex with copper acetate was synthesized and characterized by some spectral analyses. The copper(Ⅱ) ion is six-coordinated and exhibites octahedral coordination geometry, the coordination atoms are four nitrogen atoms from two (L) ligands and two carboxyl oxygen atoms from two acetic acid groups, respectively. After studying the interaction of the complex with calf thymus DNA through UV and fluorescence spectra, we can find that there is a strong binding and a large affinity berween the complex and calf thymus DNA. CCDC: 649416.     

［Cd(CHZ)3］(ClO4)2的制备和分子结构研究

本文报道了高氯酸三碳酰肼合镉(Ⅱ)的制备方法和分子结构。该配合物结构式为［Cd(CHZ)₃］(ClO₄)₂。晶体属单斜晶系,P2₁/n空间群。晶体学参数为：a=1.0281(1) nm, b=0.8617(1) nm, c=2.1360(1) nm,β=100.53°, V=1.8604(3) nm³; Z=4, Dc=2.076 g·cm^-3, μ(Mo, K_α)=15.43 cm^-1。经全矩最小二乘法对非氢原子坐标和温度因子进行修正。最终偏离因子R=0.0296。在该配合物中,碳酰肼(CHZ)分子作为双齿配体,由羰基氧原子和1位氮原子与Cd配位,形成五员平面螯合环,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高氯酸根离子,通过库仑力与内界结合在一起。     

Preparation,Structural Characterization and the Molecular Structure of 2,3,5-Trinitro-<Emphasis Type="Italic">p</Emphasis>-xylene

2,3,5-trinitro-p-xylene (TPX) is synthesized by nitration of p-xylene in mixed acid of nitric and sulfuric acid. Single crystal of TPX is cultured from DMF solution using a slow cooling method. The compound is characterized by FT-IR, ¹H NMR and MS techniques. The crystal structure is determined by X-ray⁴ single-crystal diffraction analysis. The crystal belongs to the monoclinic system with space group P_n. Its unit cell parameters are as follows: a = 0.8271(2), b = 0.6011(1), c = 1.0487(2) nm, β = 105.42(2)^∘, V = 0.50263(2) nm³, D_c = 1.593 g/cm³, Z = 2, F(0 0 0) = 248. The molecular structures of TPX have been calculated at the B3LYP/6-31G^** and B3LYP/6-311G^** levels of theory, and its frequencies analysis have also been accomplished at the same level of theory. The thermal decomposition process of the compound was studied using DSC and TG-DTG techniques. The predicted nitro group vibrations with B3LYP/6-311G^** calculation considerably agree with the observed frequencies. The calculated results propose that the structural parameters from the theory are close to those of the crystal structure from the experiments.     

酰胺型三足体铜配合物[CuL][CuCl2(NO3)2]的合成及晶体结构

The title complex， [CuL][CuCl₂(NO₃)₂] [L=N，N，N′，N′，N″，N″-Hexaisopropyl-2， 2′， 2″-Nitrilotris(2，1-ethoxy)triacetamide]， has been synthesized by using an amide-type tripodal ligand with Cu(NO₃)₂ and then characterized by X-ray single crystal structure analysis. It belongs to monoclinic，space group P2₁/c with a=1.522 7(2) nm，b=1.277 8(2) nm， c=2.184 5(4) nm， β=93.680(10)°， V=4.241 6(12) nm³， Z=4， D_c=1.401 Mg·m^-3， μ=1.189 mm^-1， F(000)=1 880， and final R₁=0.050 9， wR₂=0.125 3. The results show a Cu(Ⅱ) ion was encapsulated by the three chains of the cup-like heptadentate ligand and four-coordinated by the central nitrogen atom and three oxygen atoms from the ligand. CCDC: 648900.