三核铜（Ⅰ）配合物的合成与结构

三核铜（Ⅰ）配合物的合成与结构杨瑞娜吴生林王冬梅金斗满（河南化学研究所郑州４５０００３）罗保生谌了容（武汉大学分析测试中心４７００５３）含双齿膦配体ｄｐｐｍ（双二苯基膦甲烷）的低氧化态金属配合物由于其特殊的成键性质，反应性和催化性能而日益受到化学专家...     

酰胺型配体铜、锌、银配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了5个配合物[CuLCl₂]·CH₃COCH₃ (1)、[ZnLCl₂]·CH₃COCH₃ (2)、[ZnL(NO₃)₂]·0.5CH₃COCH₃ (3)、[AgL₂]ClO₄ (4)和[AgL₂]BF₄ (5)(L=2-(5-氯-8-喹啉氧基)-1-(吡咯烷-1-基)乙酮)。配合物1和2同构,五配位的中心金属离子采取扭曲的四方锥配位构型,与来自配体L的2个氧原子和1个氮原子及2个氯离子配位。而在配合物3中,锌离子与1个三齿配位的配体L,1个单齿配位的硝酸根和1个双齿配位的硝酸根配位,配位构型为扭曲的八面体。配合物4和5中,中心金属与配体的比例为1:2。银离子与2个三齿配位的配体L配位,采取扭曲的八面体配位构型。乙腈溶液中,配合物1、2、4和5在410 nm处的最大荧光发射峰与配体L相似。而配合物3由于配体到锌离子之间的能量转移,最大荧光发射峰红移至430 nm。     

酰胺型配体铜、锌、银配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了5个配合物[CuLCl₂]·CH₃COCH₃（1）、[ZnLCl₂]·CH₃COCH₃（2）、[ZnL（NO₃）₂]·0.5CH₃COCH₃（3）、[AgL₂]ClO₄（4）和[AgL₂]BF₄（5）（L=2-（5-氯-8-喹啉氧基）-1-（吡咯烷-1-基）乙酮）。配合物1和2同构,五配位的中心金属离子采取扭曲的四方锥配位构型,与来自配体L的2个氧原子和1个氮原子及2个氯离子配位。而在配合物3中,锌离子与1个三齿配位的配体L,1个单齿配位的硝酸根和1个双齿配位的硝酸根配位,配位构型为扭曲的八面体。配合物4和5中,中心金属与配体的比例为1∶2。银离子与2个三齿配位的配体L配位,采取扭曲的八面体配位构型。乙腈溶液中,配合物1、2、4和5在410 nm处的最大荧光发射峰与配体L相似。而配合物3由于配体到锌离子之间的能量转移,最大荧光发射峰红移至430 nm。     

三个包含酰胺型配体铜/锌配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了3个配合物[CuLCl₂]·CH₃CN(1),[CuLBr₂]·CH₃CN(2)和[ZnL(NO₃)₂]·CH₃CN(3)(L=2-(5-氯-8-喹啉氧基)-1-(吡咯烷-1-基)乙酮)。在配合物1和2中,五配位的铜离子采取扭曲的四方锥配位构型,与来自配体L的2个氧原子和1个氮原子及2个卤离子配位。而在配合物3中,锌离子与1个三齿配位的配体L,1个单齿配位的硝酸根和1个双齿配位的硝酸根配位,配位构型为扭曲的八面体。乙腈溶液中,配合物1和2在410 nm处的最大荧光发射峰与配体L的相似,强度有所降低。而配合物3由于配体到锌离子之间的能量转移,最大荧光发射峰红移至430 nm。     

三个包含酰胺型配体铜/锌配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了3个配合物[CuLCl₂]·CH₃CN （1）,[CuLBr₂]·CH₃CN （2）和[ZnL（NO₃）₂]·CH₃CN （3）（L=2-（5-氯-8-喹啉氧基）-1-（吡咯烷-1-基）乙酮）。在配合物1和2中,五配位的铜离子采取扭曲的四方锥配位构型,与来自配体L的2个氧原子和1个氮原子及2个卤离子配位。而在配合物3中,锌离子与1个三齿配位的配体L,1个单齿配位的硝酸根和1个双齿配位的硝酸根配位,配位构型为扭曲的八面体。乙腈溶液中,配合物1和2在410 nm处的最大荧光发射峰与配体L的相似,强度有所降低。而配合物3由于配体到锌离子之间的能量转移,最大荧光发射峰红移至430 nm。     

蝎型螯合配合物在生物功能分子模拟方面的应用

蝎型螯合配合物结构新颖，功能齐全。本文概述了它在模拟碳酸酐酶，亚硝酸盐还原酶和血蓝蛋白方面的应用。     

三嗪吡唑类铜配合物的合成、结构及光谱研究

以三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(bpz*eaT)为配体,在无水乙醇和甲醇溶剂中,合成了2个配合物Cu2(mpz*eaT-EtO)2(N3)2Cl2(1)和Cu2(mpz*eaT-MeO)2(N3)4(2)(mpz*eaT-EtO:2-(3,5-二甲基吡唑)-4-乙醇-6-二乙基胺-1,3,5-三嗪;mpz*eaT-MeO:2-(3,5-二甲基吡唑)-4-甲醇-6-二乙基胺-1,3,5-三嗪)。通过元素分析、红外光谱、紫外光谱、热重分析以及X-ray单晶衍射方法对配合物进行了表征,并分析了其光谱及结构特征。晶体结构表明,配合物1属于三斜晶系,P1空间群,a=0.994 9(2)nm,b=1.021 6(2)nm,c=1.148 0(2)nm,α=115.11(3)°,β=106.99(3)°,γ=100.39(3)°,V=0.946 0(3)nm3,Z=1;配合物2属于单斜晶系,P21/c空间群,a=1.546 4(5)nm,b=1.400 8(5)nm,c=0.890 5(3)nm,β=103.227(5)°,V=1.877 9(10)nm3,Z=2。配合物1和2中的中心铜原子均为五配位,形成扭曲的四角锥构型。     

三嗪吡唑类铜配合物的合成、结构及光谱研究

以三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(bpz^*eaT)为配体,在无水乙醇和甲醇溶剂中,合成了2个配合物Cu₂(mpz^*eaT-EtO)₂(N₃)₂Cl₂(1)和Cu₂(mpz^*eaT-MeO)₂(N₃)₄(2)(mpz^*eaT-EtO：2-(3,5-二甲基吡唑)-4-乙醇-6-二乙基胺-1,3,5-三嗪;mpz^*eaT-MeO：2-(3,5-二甲基吡唑)-4-甲醇-6-二乙基胺-1,3,5-三嗪)。通过元素分析、红外光谱、紫外光谱、热重分析以及X-ray单晶衍射方法对配合物进行了表征,并分析了其光谱及结构特征。晶体结构表明,配合物1属于三斜晶系,P1空间群,a=0.9949(2)nm,b=1.0216(2)nm,c=1.1480(2)nm,α=115.11(3)°,β=106.99(3)°,γ=100.39(3)°,V=0.9460(3)nm³,Z=1;配合物2属于单斜晶系,P2₁/c空间群,a=1.5464(5)nm,b=1.4008(5)nm,c=0.8905(3)nm,β=103.227(5)°,V=1.8779(10)nm³,Z=2。配合物1和2中的中心铜原子均为五配位,形成扭曲的四角锥构型。     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH₃OH)](OTf)}_n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH₃OH}_n(2)和[Cu(HL2)(CH₃OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH₃OH)](OTf)}_n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH₃OH}_n(2)和[Cu(HL2)(CH₃OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。     

Syntheses,Structures and Spectroscopic Studies of Dimolybdenum Complexes Containing Bridging Butyrate and Phosphine Ligands

By reactions of Mo₂(O₂CPrⁿ)X₂(PPh₃)₂ (X = Cl, 1 ; X = Br, 2 ) with Ph₂PCH₂CH₂P(Ph)CH₂CH₂PPh₂ (etp) in CH₂X₂, the quadruply bonded complexes containing bridging butyrate and tridentate phosphine ligands of the type Mo₂(O₂CPrⁿ)X₃(η³‐etp) (X = Cl, 3 ; X = Br, 4 ) were prepared. Their UV‐vis and³¹P{¹H}‐NMR spectra have been recorded and the structures of 1 and 2 have been determined by X‐ray crystallography. Crystal data for 1 : space group P2₁/c, a = 9.708 (2)Å, b = 18.491 (4)Å, c= 12.688 (3)Å, β = 110.76 (3)°, V = 2130 ų, Z = 2, with final residuals R = 0.0441 and Rw = 0.0519. Crystal data for 2 : space group P2₁/c, a = 9.737 (1)Å, b = 18.632(1)Å, c = 12.680(1)Å, β= 110.27 (1)°,V = 2158.2 (3) ų, Z = 2, with final residuals R = 0.0322 and Rw = 0.0481. The δ → δ* transition energies, ³¹P{¹H}‐NMR chemical shifts and the coupling constants are dependent on the natures of the halogen atoms and the carboxylate ligands. The through metal‐metal couplings |³J_{P‐Mo‐Mo‐P}| for complexes of the type Mo₂(O₂CR)X₃(η³‐P₃), which contain η³‐polydentate phosphine ligands are about 20 ± 2 Hz.     

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I…     

Syntheses,Structures and Anticancer Activity of NNO‐Tridentate Schiff Base Copper(II) Complexes

A series of heteroleptic copper(II) complexes [Cu( ^R QYMP )(Py]] ( 1a ‐ 4d ) supported on NNO‐tridentate Schiff base ( ^R QYMP ‐H) and bipyridine (Py=bpy, a ; phen, b ; dpq, c ; dppz, d ) co‐ligands have been synthesized and characterized. X‐ray crystal structural studies of complexes 1b , 2c , 3d and 4a displays that these complexes are mononuclear with a distorted square pyramidal geometry around the copper center. Cytotoxicity results indicate that all of these complexes have much higher activity against HeLa, SCC15, BCC and Ca9‐22 cancer cell lines as compared to cisplatin. Further, copper complex bearing suitable bulky group Schiff base ligands with dppz co‐ligand could be considered in designing efficient metalbased anticancer agents.     

Syntheses and Crystal Structures of Mono- and Binuclear Copper( Ⅱ ) Mixed-ligand Complexes Involving Schiff Base

The mononuclear copper(Ⅱ) complex [Cu(L)(2-AP)] 1 and binuclear copper(Ⅱ)complex [Cu(L)(py)]2 2 (L = C1oH1 1O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine)with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1: orthorhombic, space group Pbca with a = 11.921(4), b = 15.816(6), c = 17.076(6) (A), V=3219.7(19) (A)3, C15H17CuN3O5S, Z = 8, Mr = 414.92, Dc = 1.712 g/cm3,μ(MoKα) = 1.520 mm-1,F(000) = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I ＞ 2σ(I);and crystal data for 2: monoclinic, space group P21/c with a = 7.929(3), b = 17.038(5), c = 11.734(4)(A), β = 98.162(6)°, V = 1569.1 (9) (A)3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm3, F(000)= 820,μ(MoKα) = 1.554 mm-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections (I ＞ 2o(I)). The molecular structure of complex 1 consists of one tetra-coordinated Cu(Ⅱ) atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper(Ⅱ) structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.     

两个双核稀土金属配位聚合物的溶剂热合成、晶体结构及荧光性质

以顺丁烯二酰肼（MH）为配体,通过溶剂热法合成了配位聚合物[Dy₂（MH）₆]_n·0.5DMF（1）和[Eu₂（MH）₆]_n（2）。通过红外光谱、X射线粉末衍射、X射线单晶衍射表征了2个晶体的结构。配合物1和2都是三斜晶系,P1空间群。以双核结构为顶点作图得到配合物的空间拓扑结构,拓扑类型为tsi。配合物的热重分析结果表明2个配合物在315℃左右仍有较好的热稳定性。固体荧光结果表明配合物2在激发波长为375 nm时有对应Eu³⁺的⁵D₀→⁷F_J（J=0~4）能级能量的5个发射峰,最强发射峰波长为616 nm,归属为Eu³⁺的⁵D₀→⁷F₂能级跃迁。     

两个双核稀土金属配位聚合物的溶剂热合成、晶体结构及荧光性质

以顺丁烯二酰肼(MH)为配体,通过溶剂热法合成了配位聚合物[Dy2(MH)6]n·0.5DMF(1)和[Eu2(MH)6]n(2)。通过红外光谱、X射线粉末衍射、X射线单晶衍射表征了2个晶体的结构。配合物1和2都是三斜晶系,P1空间群。以双核结构为顶点作图得到配合物的空间拓扑结构,拓扑类型为tsi。配合物的热重分析结果表明2个配合物在315℃左右仍有较好的热稳定性。固体荧光结果表明配合物2在激发波长为375 nm时有对应Eu~(3+)的5D0→7FJ(J=0~4)能级能量的5个发射峰,最强发射峰波长为616 nm,归属为Eu~(3+)的5D0→7F2能级跃迁。     

Syntheses,Crystal Structures,and Antibacterial Activities of Four Schiff Base Complexes of Copper and Zinc

Four Schiff base complexes, [Cu₂(L1)₂(μ‐NCS)₂] ( 1 ), [Cu₂(L2)₂(μ‐N₃)₂] ( 2 ), Cu[Cu(CH₃COO)(L3)]₂ ( 3 ), and [Zn{Zn(C₃H₄N₂)(L3)}₂(NO₃)](NO₃) ( 4 ) (where L1 = 2‐[(pyridin‐2‐ylmethylimino)methyl]phenol, L2 = 1‐[(pyridin‐2‐ylmethylimino)methyl]naphthalen‐2‐ol, and L3 = bis(salicylidene)‐1, 3‐propanediamine), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar di‐nuclear complexes, which are located at crystallographic inversion centers (with the center of the central Cu₂N₂ ring). In 1 , each copper atom has a slightly distorted square pyramidal configuration, coordinated by two nitrogen atoms and one oxygen atom from L1 and another two terminal nitrogen atoms from two bridging thiocyanate anions. The Cu···Cu separation is 3.466(3) Å. The structure of 2 is similar to that of 1 , with Cu···Cu separation of 3.368(2) Å. Both 3 and 4 are linear tri‐nuclear complexes. In 3 , the central Cu²⁺ ion is located on an inversion centre and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands (L3) in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Cu²⁺ ions is irregular‐square pyramidal, with two O and two N atoms of L3 in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Cu²⁺ ions are mutually trans. The Cu···Cu separation is 3.009(3) Å. In 4 , the coordination configuration of the central and the terminal zinc atoms are similar to that of the 3 , with Zn···Zn separation of 3.153(4) Å. The three Schiff bases and the corresponding three copper complexes exhibit good antibacterial properties, while the zinc complex 4 has nearly no.