Comparative Studies of Some Novel Cu(II) Polymeric Complexes Derived from Cyanoacetylhydrazine (CAH;L). The Role of Solvents Used on the Structure and Geometry of the Isolated Cu²⁺Complexes

Novel polymeric Cu2+ complexes derived from the reaction of cyanoacetylhydrazine (CAH;L) with CuCl2•2H2O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, 1H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that CAH behaves in different ways towards the coordination of the Cu2+ ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu2+ ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu2+ complexes. EPR studies indicate the existence of polymeric complexes depending on the results of g-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.

FERROMAGNETICALLY COUPLED Gd(III)Cu(II)Gd(III)TRINUCLEAR COMPLEXES

Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.

SYNTHESIS AND CARACTERIZATION OF TERNARY COMPLEXES CONTAINING Cu(II),L-HISTIDINE AND NUCLEOTIDE

The ternary complexes containing Cu(II),L-His and nucleotide (5'-GMP and 5'-IMP)were synthesized and characterized.IR and ~1H NMR spectra show that Cu(II)binds to carboxylate oxygen and imidazole nitrogen of L-His and purine N_7 of 5'-GMP and 5'-IMP.The interaction of Cu(II)with Po_3^(2-)of 5'-GMP is present,but that for 5'-IMP is not present.

Two Cu(II)-Nitronyl Nitroxide Complexes Including Cyclic Dimer: Synthesis, Structures and Magnetic Interactions

Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)2]3(NITmPhO3Py)2}n (1) and [Cu(hfac)2 (NIToPhO3Py)]2 (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)2]3(NITmPhO3Py)2}n due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)2]2(NITmPhO3- Py)2} via the bridging unit [Cu(hfac)2];complex 2 presented a binuclear cyclic structure [Cu(hfac)2]2(NIToPhO3Py)2. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2.

Synthesis of Branched Polyethylene via Bulky α-Diimine Nickel(II)-Catalyzed Ethylene Chain-Walking Polymerization

The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex with Tridentate Schiff Base and Azido Bridge

A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.

Crystal Structures of Co(Ⅱ) and Cu(Ⅱ) Complexes and Ammonium Salt Involving Ethylenediamine

The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.

Synthesis,Structure and Properties of a Novel Copper(Ⅱ)-2,2'- biimidazole Complex-supported Compound:[Cu(H_2biim)_2]{[Cu(H_2biim)_2 ]_2[H_(10)W_(12)O_(44)]}·8H_2O

A new copper（II）-2,2＇-biimidazole metal-organic POMs-supported compound [Cu（H2biim）2]{[Cu（H2biim）212[H10W12O44]}＇8H2O （H2biim = 2,2＇-biimidazole） has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800（2）, b = 13.437（3）, c = 13.685（3） A, V = 1922.5（7） A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F（000） = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections （I 〉 2σ（I））. X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu（H2biim）2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.＇-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex [Cu(C_(12)H_(17)N_2O)(NCS)]_2 with Tridentate Schiff Base Ligand N-(Salicylidene)-3-dimethylaminopropylamine

A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.

Synthesis,Structure and Magnetism of Two Cu(Ⅱ) 4,5-Dichlorophthalate Complexes

Two 4,5-dichlorophthalate-based metal complexes, {[Cu（bipy）（dcpa）].H2O}n, （1） and {[Cu2Coipy）2（Hdcpa）3]·H2O·C2H5OH.Hdcpa} （2, H2dcpa = 4,5-dichlorophthalic acid and bipy = 2,2＇-bipyridine）, were synthesized and characterized structurally and magnetically. Complex 1 is of orthorhombic system, space group Fdd2 with a = 20.5821（8）, b = 20.9013（12）, c = 17.0270（7） A, V= 7324.9（6） A3, Dc = 1.707 g/cm3, Mr = 470.74, Z = 16, F（000） = 3792, p = 1.519 mm^-1, the final R = 0.0223 and wR = 0.0549 for 9239 observed reflections with I〉 2σ（I）. Complex 2 crystallizes in triclinic, space group P1 with a = 14.1439（12）, b = 14.2981（12）, c = 15.1054（14） A, a = 72.121（2）, β = 77.703（2）,γ = 81.829（2）°, V= 2830.9（4） A3, Dc = 1.689 g/cm3, M,. = 1439.55, Z = 2, F（000） = 1452,μ = 1.207 mm^-1, the final R = 0.0536 and wR = 0.0981 for 16422 observed reflections with 1 〉 2σ（I）. Complex 1 exhibits a diamond-like framework with centrosymmetric binuclear subunits extended by pairs of doubly deprotonated dcpa2- linkers. By contrast, 2 is an asymmetric binuclear entity bridged by carboxylate group of mono deprotonated Hdcpa- ligands. Weak anti- and ferromagnetic interactions are respectively mediated in the carboxylate aggregated binuclear subunits of 1 and 2.

SYNTHEIS, SITUCTURE AND CHARACTERIZATION OF BINUCLEAR Cu(II)COMPLEX[Cu(C_6H_5COO)_2(C_5H_6N_2)]_2.(C_4 H_8O)_2

At room temperature,dibenzoyl peroxide undergoes oxidative addition on metallic Copper Powder and 2-aminopyridine in a solvent(acetone and tetrahydrofuran), which affords the product as a binuclear Cu(II)complex [Cu (C5 H5 COO)2(C5 H5 N2)]2. (C4 H5 O)2. The structure of the complex was characterized by elemental analyses. IR spectra, TG-DTA. The structure of the compound has been solved by direct method and Fourier synthesis, and refined by block-diagonal and full matrix least-squares method to a final R of 0.04329 for 3671 independent reflection of I>e(I). The crystals are triclinic, C46H45N4O10Cu2.Z=1, Mr=943.93, space group P-1, with cell parameters, a=10.806(1); b=11.169(3);c=11.729(2)A; α=71.99(2),β=89.38(1)°; γ=81.37(1); V=1330.1A3; Dc=1.172g.cm-3;μ=8.5cm-1. The copper(II) ion is coordinated by four bridging bidentate benzoate and two 2-aminopyridine to form dimeric molecules.

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.

Synthesis and Crystal Structure of Cu(II) Complex with 2,9-Bis(n-2',5'-diazaheptanyl)-1,10-phenanthroline

The Cu(II) complex with the ligand 2,9-bis(n-2?5?diazaheptanyl)-1,10-phenan- throline (L) has been synthesized and characterized by single-crystal X-ray diffraction. It crys- tallizes in the monoclinic system, space group P21/n with a = 12.549(4), b = 13.544(4), c = 16.767(5) ? = 107.179(5), C22H32Cl2N6CuO8, Mr = 642.98, V = 2722.5(13) 3, Z = 4, Dc = 1.569 g/cm3, ?= 1.056 mm-1, F(000) =1332, the final R = 0.0733 and wR = 0.1581. The X-ray analysis revealed that the Cu(II) ion is coordinated by six nitrogen atoms of the ligand, in which two nitrogen from phenanthroline and another two from the imine groups near phenanthroline are in the equatorial plane while the two from imine groups at the end of both arms in the axial positions. The coordination geometry can be described as a compressed octahedron.

新型一维梯状双链配位聚合物{[Cu(malate)(2,2′-bipy)]·3H_2O}_∞的合成、晶体结构与表征

合成了铜(II)与羟基丁二酸和2,2′-联吡啶形成的配位聚合物{[Cu(malate)(2,2′-bipy)]?3H2O}∞(其中malate=羟基丁二酸根,2,2'-bipy=2,2'-联吡啶),通过X射线衍射测定了单晶结构,并进行了元素分析、红外光谱、紫外光谱、热分析等研究.配合物属单斜晶系,空间群P2(1)/c;晶胞参数a=0.70132(10)nm,b=1.9730(3)nm,c=1.18998(16)nm,β=94.551(3)°;Z=2;最终偏离因子R=0.0483.配合物中每个铜(II)原子与来自2,2'-联吡啶的两个氮原子和两个羟基丁二酸根的三个氧原子配位,形成畸变的三角双锥结构单元.每个羟基丁二酸根以R构型方式桥联两个三角双锥结构单元,沿a轴方向无限延伸形成一维链.两条平行链以面对面的方式重叠,彼此吡啶环之间存在强的π-π相互作用,加之C吡啶环—H…O羧基弱相互作用形成新颖的梯状双链结构,比邻的梯状双链又通过分子间O羟基—H…O羧基氢键沿a轴方向共同构筑了具有隧道的三维结构.

含四氮杂大环的双(O,O'-二(2-苯乙基)二硫代磷酸根)合镍(II)或铜(II)配合物的合成和晶体结构

合成了含四氮杂大环hmta(hmta = meso-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷 )和O,O-二(2-苯乙基)二硫代磷酸根的配合物 [Ni(hmta){SSP(OCH2CH2Ph)2}2] 1和 [Cu(hmta){SSP(OCH2CH2Ph)2}2] 2 , 并测定了它们的晶体结构。配合物1属单斜晶系,空间群为P21/c,晶胞参数为: C48H72N4O4P2S4Ni, a = 9.827(3), b = 19.430(6), c = 13.932(3) ? b = 99.99(2), Mr = 1017.99, V = 2620(1) 3, Z = 2, Dc = 1.285 g/cm3, = 0.635 mm-1, F(000) = 1076, 最终的偏离因子为R = 0.0434, wR = 0.1078, 相应的可观测反射数为2306; 配合物2属单斜晶系, 空间群为P21/c, 晶胞参数为: C48H72N4O4P2S4CuO25, a = 9.730(4), b = 19.513(4), c = 14.031(3) ? b = 99.97(3), Mr = 1022.82, V = 2624 (1) 3, Z = 2, Dc = 1.295 g/cm3, = 0.681 mm-1, F(000) = 1086, 最终的偏离因子为R = 0.0465, wR = 0.1222, 相应的可观测反射数为2492。结构测定表明:两配合物中的配体 (PhCH2CH2O)2PS2-均为单齿配体,金属离子与硫和氮形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性; 同时晶胞中配合物的两配体之间形成了2种N-H贩稴氢键。

席夫碱Cu(Ⅱ)配合物与鲱鱼精DNA的相互作用研究

采用电化学和光谱法,研究了糠醛缩对氨基苯磺酸席夫碱Cu(Ⅱ)配合物与鲱鱼精DNA的相互作用。结果发现:糠醛缩对氨基苯磺酸席夫碱Cu(Ⅱ)中加入DNA后,氧化还原峰电流降低,式量电位正移;席夫碱Cu(Ⅱ)配合物使DNA的最大吸收峰强度增强,DNA使席夫碱Cu(Ⅱ)配合物的荧光强度增强。表明席夫碱Cu(Ⅱ)配合物以嵌插模式与DNA作用。

硫脲壳聚糖-Cu配合物的制备、表征及其抑菌活性

利用IR、UV、TG-DTA和XRD手段,对合成的硫脲壳聚糖-Cu配合物进行表征,研究壳聚糖、硫脲壳聚糖及硫脲壳聚糖-Cu配合物对大肠杆菌、金黄色葡萄球菌的抑菌性能。结果表明:硫脲壳聚糖-Cu配合物的抑菌性能优于单一的壳聚糖和硫脲壳聚糖。

2-羟基-1-萘甲醛缩邻苯二胺双希夫碱Cu(Ⅱ)配合物的合成及其晶体结构

采用Cu(Ⅱ)盐与2-羟基-1-萘甲醛缩邻苯二胺双希夫碱(H2L)在二氯甲烷-乙醇溶液中首次合成了2-羟基-1-萘甲醛缩邻苯二胺双希夫碱Cu(Ⅱ)配合物(1),其结构经IR,元素分析和X-射线单晶衍射表征。1属单斜晶系,空间群P2(1)/n,晶胞参数a=11.046 2(11)nm,b=13.6721(12)nm,c=16.6838(15)nm,β=103.7430(10)°,V=2447.5(4)nm3,Z=4,Dc=1.496 Mg.m-3,F(000)=1140,μ=0.93 mm-1,对I>2σ(I)衍射点的最终偏差因子R1=0.079,ωR2=0.201 4。

可溶性铜盐配合物Cu(OH)_4^(2-)氧化扁桃酸制备香兰素

以可溶性铜盐配合物Cu(OH)2-4作为氧化剂,选择性氧化扁桃酸制备香兰素。当二价铜盐Cu SO4·5H2O与扁桃酸的摩尔比值为2.5,体系p H=13.5,温度为95℃,反应时间为8 h,香兰素收率可达95.6%。二价铜盐在H2SO4溶液中由H2O2氧化Cu2O再生,再生后的二价铜盐的活性无明显下降,10次循环后香兰素的收率仍可达95.4%。

一种新型用于原子转移自由基聚合过程的Cu(I)络合物的研究

将以三齿2,6 双(苯并咪唑)吡啶为配体的Cu(I)离子络合物用作A TRP引发体系的组分之一,并成功地实现了对烯类单体的自由基聚合.聚合过程具有明显的ATRP聚合特征.和几种具不同结构胺配体构成的Cu(I)络合物的聚合速度结果相比较,本工作的结果基本符合烷基胺≈吡啶>亚胺>芳基胺的序列关系.