A 2D Wavy Parquet Architecture Based on the Biphenyl-3,3',4,4'-tetracarboxylic Acid and Bis(2-benzimidazole)alkanes Ligands

A double-T-shaped ligand （H4BPTC） and bis（2-benzimidazole）alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn（BPTC）0.5（H2C2EIm）（H2O）]n （1, C24H18ZnN4O5, Mr = 507.79, H4BPTC = biphenyl-3,3＇,4,4＇-tetracarboxylic acid, H2C2EIm = 2,2＇-（1,2-ethanediyl）-bis（1H-benzi- midazole）, which was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 1.1844（5）, b = 1.4019（5）, c = 1.4026（5） nm, β = 108.359（5）°, V = 2.2104（15） nm3, Z = 4, Dc = 1.526 g/cm3, μ（MoKα） = 1.156 mm-1, F（000） = 1040, S = 1.038, the final R = 0.0427 and wR = 0.0793 for 3834 reflections with I 2σ（I）. The compound units are linked through BPTC ligands into a wavilness parquet 2D layer and further connected into a 3D framework via π-π packing interactions between the adjacent H2C2EIm ligands and weak N-H…O hydrogen bonding between uncoordinated carboxylate and the nitrogen atoms of H2C2EIm as well as the free water molecules.

Synthesis of New Chiral C_2-Symmetrical Bis(oxazoline) Compounds

New chiral C_2-symmetrical bis(oxazoline) compounds bearing one isobutyl-, secbutyl-, benzyl- or isopropyl-substituent at the 4-position have been prepared and characterized.

Controlled Self-assembly of Two Coordination Polymers via subtly Varying Bis(2-methyl imidazole) Ligands:from 3-Connected(6,3) Net to 4-Connected sql Net

Two coordination polymers constructed from 3,4-thiophenedicarboxylic acid and bis（2-methyl imidazole） ligands, namely, {[Cd2（tdc）2（bip）2]·7H20}n （1） and [Cd（tdc）（bib）]n （2） （Hgtdc = 3,4-thiophenedicarboxylic acid, bip = 1,3-bis-（imidazol-2-methyl）propane and bib = 1,4-bis（imidazol-2-methyl）butane）, have been synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analyses reveal that 1 exhibits a two-dimensional （2D） layered network with 3-connected （6,3） topology, which is further connected into a three- dimensional （3D） supramolecular structure by intermolecular hydrogen bonds. However, 2 features a 2D network which can be rationalized as a 4-connected sql net. The results indicate the subtle difference of auxiliary bis（imidazol-2-methyl） ligands may lead to diverse architectures. Moreover, they exhibit luminescence emission in the solid state at room temperature.

Convenient Synthesis of Bis(oxazoline) Dicarboxylate Derivatives.

The synthesis of bis(oxazoline) dicarboxylate derivatives was investigated. Diethyl-aminosulfur trifluoride (DAST) was used as a convenient cyclization reagent in the synthesis of bis(oxazoline) dicarboxylate derivatives, which can not be obtained by the general method using MsCl and Et3N as dehydrating cyclization reagent.

Flexible Bis(benzimidazole)-based Ligands Directed the Structure Characteristics of Coordination Polymers Based on Diphenic Acid Co-ligands:Syntheses, Structures and Properties

Two new coordination polymers [Cu_2(bbim)(dpa)_2(C_2H_5OH)_2](1), [Co(dpa)_2(bbbm)](2)(H_2dpa = diphenic acid, bbim = 1,1?-(1,6-hexanediyl)bis-1H-benzimidazole, bbbm = 1,1?-(1,4-butanediyl)bis-1 H-benzimidazole) constructed from bis(benzimidazole)-based ligands with different lengths and diphenic acid co-ligand have been synthesized under solvothermal conditions.Complex 1 possesses Cu-dpa helical chains. The adjacent chains are connected by the bbim ligands into two-dimensional(2D) 3-connected(63) topology. Differently, the layer structure of 2 was consisted by one-dimensional chains containing alternated 8-and 18-membered rings. Furthermore,the thermal stability and fluorescence property for all crystalline materials have been investigated.

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles)Ligands

Two compounds have been obtained by the reaction of metal（Cu（II））, 4,4＇-bis（imidazol-l-yl）diphenyl thioether（BIDPT） with two carboxylic acids, 4,4＇-oxydibenzoic acid（H2oba） and phthalic acid（H2pht）. The crystal structures of the resulting compounds, namely {[Cu（BIDPT）（oba）]·H2O}n（1） and {Cu（BIDPT）（pht）}n（2）, have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310（3）, b = 10.7791（1）, c = 19.3913（2）A, V = 5817.0（3） ？3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678（2）, b = 11.0259（1）, c = 22.906（2） A, β = 97.727（2）o, V = 4571.8（8） A3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional（2D） wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

A new complex [Zn（4-nph）（bib）]（2n）·nH2O（1） has been obtained by the reaction of metal（Zn（Ⅱ））,1,4-bis（imidazol-1-yl）-butane（bib） with 4-nitrophthalic acid（4-H（2nph））.The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487（3）,β = 72.529（3）,γ = 79.991（3）°,V = 2009.8（5）A^3 and Mr = 945.47.Complex 1 shows a three-dimensional（3 D） framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.

Crystal Structures of Dinuclear Copper(Ⅱ) Complexesof bis (1,4,7-triazacyclononane) Ligands Containing Rigid Bridging Groups

Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.

Mass Spectrometric Fragmentation of 1,8-Bis[4-substituted- (oxazolin-2-yl)] anthracenes: Ring-contraction Rearrangement of Oxazoline Ring under Electron-Impact Ionization Conditions

The mass spectrometric fragmentation of 1,8-bis [ 4-substituted （oxazolin-2-yl） ] anthracenes （AnBOXes） was investigated by using mass-analyzed ion kinetic energy spectrometry under electron-impact ionization conditions. All the compounds could undergo a ring contraction by the loss of an RCH = CH2 molecule to form 1-oxazirinyl-8-（oxazolin- 2-yl） anthracene ions, which could further lose an R radical, followed by the loss of oxazoline. These ions could also eliminate an R radical and subsequently undergo ring-contraction rearrangements to lose a CHCH2O fragraent and an epoxide molecule, respectively. The ions that are formed could further lose CHCH2O and CH2 = CH fragments. Several ring-contraction rearrangements of the oxazoline ring were observed under electron-impact ionization conditions.

Asymmetric Induction of Chiral 1,1'-Bis(oxazolinyl)ferrocenes as Ligands in Metal-Catalyzed Cyclopropanation and Diels-Alder Reactions

Four chiral 1,1?bis(oxazolinyl)ferrocenes(1a-1d) have been prepared and used as ligands in the copper catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate (EDA) and the magnesium catalyzed Diels-Alder reaction between 3-acryloyl-2-oxazolidinone and cyclopentadiene. Enantioselectivities up to 24% and 41%, respectively, for cyclopropanation and Diels-Alder reaction were observed.

前列腺素D_(2)受体拮抗剂关键中间体的工艺改进

前列腺素D2受体拮抗剂是治疗哮喘和过敏性疾病的潜在药物,其关键中间体合成方法尚不成熟。以N-乙酸叔丁酯吲哚和环状苯并磺酰醛亚胺为底物,自制的新型螺环噁唑啉为配体,路易斯酸为催化剂,通过催化的傅克烷基化反应制备了前列腺素D2受体拮抗剂的关键中间体。配体筛选结果表明:不同的配体对反应的收率起到关键作用,其中螺环喹啉噁唑啉配体和三氟甲磺酸锌复合物催化的反应收率最高,且未产生开环结构的双吲哚副产物。通过对反应溶剂、底物物质的量之比和反应温度等反应条件的研究,确定了最佳的反应条件:以二氯甲烷为反应溶剂,N-乙酸叔丁酯吲哚和环状苯并磺酰醛亚胺物质的量之比为1∶1, 0℃反应时,收率最高可达97%。该工艺反应条件温和,使用了廉价且环境友好的催化剂,避免使用传统工艺中腐蚀性和易制爆物料。

基于芳基桥联双β-二亚胺配体的金属铝配合物的合成与结构表征

β-二亚胺作为一类理想的含氮单阴离子非环戊二烯基配体,可以很好的稳定低价或配位不饱和的金属配合物,而桥联的双β-二亚胺配体要比单个β-二亚胺配体多个活性位点,会以更多的方式与金属配位,该类配合物表现出更高的催化活性和更加丰富的反应性。本文利用芳基桥联双β-二亚胺配体LH_(2)(L=[μ-(1,4-C_(6)H_(4))][N(Me)CH_(2)-CH_(2)NC(Me)CC(Me)HNDipp]_(2)^(2-),Dipp=2,6-(iPr)_(2)C_(6)H_(3))和4当量的三甲基铝反应,得到了相应的双核金属铝配合物LAl_(2)Me_(4)(1)。然后通过^(1)H NMR、^(13)C{^(1)H}NMR、红外光谱和单晶X-射线衍射对该配合物进行了结构表征。

Synthesis and Potential Application of Novel C_(2)-Symmetrical Bis(ferrocenyl)P2N Ligand

A novel chiral bis(ferrocenyl) P2N ligand 1 with C2-symmetry was synthesized through a four-step procedure from (R)-N,N-dimethyl-1-ferrocenylethylamine. In a model reaction of Pd-catalyzed allylic alkylation of 1,3-diphenylprop-2-enyl acetate 6 with dimethyl malonate, good enantioselectivity (86% e.e.) was obtained.

Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand： Assembly, Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.

Two Cobalt(II) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine:Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL_2]X·H_2O (X = ClO_4^-, N

The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.

两个苯甲羟肟酸有机锡配合物的合成、结构及抗癌活性

合成了2个苯甲羟肟酸有机锡配合物:[(o-Cl-C_(6)H_(4)CH_(2))_(2)Sn(C_(6)H_(5)CONO)_(2)](1)和[(o-CH3-C_(6)H_(4)CH_(2))_(2)Sn(C_(6)H_(5)CONO)(C_(6)H_(5)COO)](2)。通过元素分析、红外光谱、核磁共振氢谱、热重分析、单晶X射线衍射等方法对配合物进行了结构表征,对其结构进行量子化学从头计算和体外抗癌活性研究。结果显示:配合物均为单锡核结构,配合物1为六配位的畸变八面体构型,配合物2为五配位的畸变三角双锥构型;配合物1对人宫颈癌细胞(HeLa)、肝癌细胞(HuH-7)和肺腺癌细胞(H1975)显示出比临床使用的顺铂强的抑制活性,而配合物2的抑制活性要弱得多。

(R,R)-环己基桥联双脒基稀土金属配合物的合成与表征

改变脒基骨架中C原子和N原子上的取代基团,可以调控脒基配体的空间位阻效应和电子效应以满足配位需求。因此,脒类化合物被广泛用作配体。手性环己基桥联双脒基配体{(R,R)-Cy-1,2-[NHCN(^(t)Bu)C_(6)H_(5)]}与离子型三胺基稀土金属配合物通过硅胺基消除反应得到了一系列结构新颖的手性环己基桥联双脒基配合物(R,R)-Cy-1,2-[NCN(tBu)C_(6)H_(5)]REN(SiMe_(3))_(2)(RE=Y(1)Er(2),Yb(3))。配合物的结构经过X-射线单晶衍射、核磁及元素分析表征,结果表明,配合物为正交晶系,空间群为P2_(1)2_(1)2_(1),配合物是由两个脒基分别以κ^(2)-N,N′,η^(1)的配位模式与金属中心成键,一个硅胺基[-N(SiMe_(3))_(2)]及一个四氢呋喃溶剂分子组成的单核五配位结构。

Modification of diphenylamine-linked bis(oxazoline) ligands: Tuning of electronic effect and rigidity of ligand skeleton

The electronic effect of diphenylamine-linked bis(oxazoline) ligands was tuned through introduction of electron-withdrawing bromo and nitro substituents onto the 4 and 4′ position. The variation of the NH bond acidity was determined by the different chemical shifts of NH. The catalytic activity and enantioselectivity of the modified ligands were tested in the asymmetric Friedel-Crafts alkylation of indole with β-nitrostyrene. The effect of ligand skeleton rigidity was also investigated through the synthesis of iminodibenzyl-linked bis(oxazoline) ligands and evaluation of their catalytic activity in Friedel-Crafts alkylation.