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1.
通过[CuL](ClO4)2(L=5,12-二甲基-1,8-二乙醇基-1,3,6,8,10,13-六氮杂环十四烷)与NH4VO3反应,得到一个钒氧多酸桥联大环铜配合物的三维配位聚合物{[CuL][VO3]2·0.67H2O}n。并对其进行了元素分析、红外光谱、紫外光谱、热重和X-射线单晶衍射测定。单晶结构测试结果表明配合物属于三方晶系,R3空间群。在晶体结构中,铜原子与大环配体上的四个氮原子和钒氧四面体[VO4]中的2个氧原子配位,形成畸变的八面体构型。钒氧多酸阴离子[V6O18]6-桥联大环配合物[CuL]2+形成一个具有一维通道的三维配位聚合物。  相似文献   

2.
以4-甲氧基水杨醛和季戊四胺进行缩合反应得到席夫碱化合物 H4L, 然后将配体H4L分别与Ni(ClO4)2·6H2O、Cu(ClO4)2在乙醇溶液中进行配位反应, 得到2个席夫碱配合物[Ni2(L)]·DMF (1)和[Cu4(L)2(DMSO)3]·2DMSO (2)。并用元素分析、FT-IR和X射线单晶衍射进行了表征。配合物12都属于三斜晶系, P1 空间群, 配合物12都为双核配合物。初步研究了配体和配合物的体外抑菌活性, 结果表明, 配体及其配合物1和2对金黄色葡萄球菌具有一定的抑菌活性。  相似文献   

3.
以配体菲咯啉取代苷脲(L), 分别与CoCl2·6H2O、CuCl2·2H2O进行配位反应, 得到2个配合物{[Co(L)(H2O)3]Cl2·2H2O}n(1)和[Cu2(L)2Cl4]·3C2H5OH(2)。并用元素分析、FTIR和X-射线单晶衍射进行了表征。晶体结构表明:配合物1属于正交晶系, P212121空间群, 每个Co(Ⅱ)的配位环境为扭曲的八面体, 分别与1个配体上菲咯啉单元的2个氮原子、另外1个配体的羰基氧原子和3个水分子配位, 配合物中每个配体 L 表现为三齿配体分别与2个Co(Ⅱ)离子配位桥联形成一维链状结构。配合物2属于单斜晶系,P21/n空间群, Cu(Ⅱ)的配位环境为扭曲的四方锥形, 分别与配体上菲咯啉单元的2个氮原子和3个氯原子配位, 3个氯原子中有2个氯原子同时和2个Cu(Ⅱ)离子配位, 从而使配合物2形成双核配合物。  相似文献   

4.
外消旋大环镍(Ⅱ)配合物[Ni (rac-L)](ClO4)2分别与l-和d-扁桃酸阴离子在乙腈/水溶液中反应,通过手性识别得到六配位的[Ni (RR-L)(S-Man)]ClO4(1)和[Ni (SS-L)(R-Man)]ClO4(2)对映异构体(L=5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷,Man=扁桃酸)。当[Ni (rac-L)](ClO4)2dl-扁桃酸阴离子反应时得到一对对映体等量存在的共聚物,其中大环配体中RRSS构型分别优先与l-和d-Man- 配位形成外消旋混合物,反应过程中发生了手性识别现象,每颗晶体均为手性对映体。当[Ni (rac-L)](ClO4)2分别与结构类似的dl-2-苯基丙酸和dl-托品酸阴离子反应时,分别得到化合物[Ni (rac-L)(dl-PPA)]ClO4(3)(PPA=2-苯基丙酸)和[Ni (rac-L)(dl-Tro)]ClO4(4)(Tro=托品酸)。X射线单晶衍射结果表明,4个配合物中Ni (Ⅱ)离子均与折叠大环配体L的4个氮原子和2个来自羧基与羟基的氧原子(12),或羧基氧原子(34)顺式配位,形成六配位八面体构型。配合物12属于一对对映异构体,分别通过[Ni (RR-L)(S-Man)]+和[Ni (SS-L)(R-Man)]+分子间氢键作用形成一维之字形链状结构。配合物12的单手性特征与圆二色(CD)谱测定结果一致。  相似文献   

5.
外消旋大环镍(Ⅱ)配合物[Ni (rac-L)](ClO4)2分别与l-和d-扁桃酸阴离子在乙腈/水溶液中反应,通过手性识别得到六配位的[Ni (RR-L)(S-Man)]ClO4(1)和[Ni (SS-L)(R-Man)]ClO4(2)对映异构体(L=5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷,Man=扁桃酸)。当[Ni (rac-L)](ClO4)2dl-扁桃酸阴离子反应时得到一对对映体等量存在的共聚物,其中大环配体中RRSS构型分别优先与l-和d-Man- 配位形成外消旋混合物,反应过程中发生了手性识别现象,每颗晶体均为手性对映体。当[Ni (rac-L)](ClO4)2分别与结构类似的dl-2-苯基丙酸和dl-托品酸阴离子反应时,分别得到化合物[Ni (rac-L)(dl-PPA)]ClO4(3)(PPA=2-苯基丙酸)和[Ni (rac-L)(dl-Tro)]ClO4(4)(Tro=托品酸)。X射线单晶衍射结果表明,4个配合物中Ni (Ⅱ)离子均与折叠大环配体L的4个氮原子和2个来自羧基与羟基的氧原子(12),或羧基氧原子(34)顺式配位,形成六配位八面体构型。配合物12属于一对对映异构体,分别通过[Ni (RR-L)(S-Man)]+和[Ni (SS-L)(R-Man)]+分子间氢键作用形成一维之字形链状结构。配合物12的单手性特征与圆二色(CD)谱测定结果一致。  相似文献   

6.
外消旋大环镍(Ⅱ)配合物[Ni (rac-L)](ClO4)2分别与l-和d-扁桃酸阴离子在乙腈/水溶液中反应,通过手性识别得到六配位的[Ni (RR-L)(S-Man)]ClO4(1)和[Ni (SS-L)(R-Man)]ClO4(2)对映异构体(L=5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷,Man=扁桃酸)。当[Ni (rac-L)](ClO4)2dl-扁桃酸阴离子反应时得到一对对映体等量存在的共聚物,其中大环配体中RRSS构型分别优先与l-和d-Man-配位形成外消旋混合物,反应过程中发生了手性识别现象,每颗晶体均为手性对映体。当[Ni (rac-L)](ClO4)2分别与结构类似的dl-2-苯基丙酸和dl-托品酸阴离子反应时,分别得到化合物[Ni (rac-L)(dl-PPA)]ClO4(3)(PPA=2-苯基丙酸)和[Ni (rac-L)(dl-Tro)]ClO4(4)(Tro=托品酸)。X射线单晶衍射结果表明,4个配合物中Ni(Ⅱ)离子均与折叠大环配体L的4个氮原子和2个来自羧基与羟基的氧原子(12),或羧基氧原子(34)顺式配位,形成六配位八面体构型。配合物12属于一对对映异构体,分别通过[Ni (RR-L)(S-Man)]+和[Ni (SS-L)(R-Man)]+分子间氢键作用形成一维之字形链状结构。配合物12的单手性特征与圆二色(CD)谱测定结果一致。  相似文献   

7.
以3-苯氧基甲基-4-(4-甲基苯基)-5-(2-吡啶基)-1,2,4-三唑(L)为配体分别合成了2个金属配合物即[Cu2L2Cl4]·2H2O (1)和 [Cd3L2(μ2-Cl)6]n·2nCH3CN (2),对其进行了红外、紫外、热重、粉末衍射、元素分析和晶体结构等表征.配合物 12 都属于三斜晶系,空间群都为P1 ,单晶结构分析表明,在配合物 1 中,中心铜(Ⅱ)原子具有畸变三角双锥构型[CuN3Cl2];配合物 2 是配位聚合物,每个重复单元有3个Cd(Ⅱ)原子和2个不同的Cd(Ⅱ)配位中心,Cd1(Ⅱ)原子具有中心对称的畸变八面体构型CdCl4N2,Cd2(Ⅱ)原子具有畸变的八面体构型CdCl4N2.  相似文献   

8.
以配体菲咯啉取代苷脲(L), 分别与CoCl2·6H2O、CuCl2·2H2O进行配位反应, 得到2个配合物{[Co(L)(H2O)3]Cl2·2H2O}n(1)和[Cu2(L)2Cl4]·3C2H5OH(2)。并用元素分析、FTIR和X-射线单晶衍射进行了表征。晶体结构表明:配合物1属于正交晶系, P212121空间群, 每个Co(Ⅱ)的配位环境为扭曲的八面体, 分别与1个配体上菲咯啉单元的2个氮原子、另外1个配体的羰基氧原子和3个水分子配位, 配合物中每个配体 L 表现为三齿配体分别与2个Co(Ⅱ)离子配位桥联形成一维链状结构。配合物2属于单斜晶系, P21/n空间群, Cu(Ⅱ)的配位环境为扭曲的四方锥形, 分别与配体上菲咯啉单元的2个氮原子和3个氯原子配位, 3个氯原子中有2个氯原子同时和2个Cu(Ⅱ)离子配位, 从而使配合物2形成双核配合物。  相似文献   

9.
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12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45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1245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。  相似文献   

10.
以2-甲基-5-(2-吡啶基)-1,3,4-噁二唑(L)为配体合成了[Cu2L2μ-Cl)2Cl2](1)和[CdL2(NO32](2),测定了X射线单晶结构,用红外光谱、紫外光谱、荧光及热重分析进行了表征。配体L和配合物2属于单斜晶系,配合物1属于三斜晶系。L,12的空间群分别为P21/c,P1C2/c。配合物1是通过2个氯原子(Cl1,Cl1i)桥联形成的双桥双核Cu(II)配合物,具有畸变四方锥构型[CuCl3N2]。配合物2具有畸变八面体构型[CdN4O2]。  相似文献   

11.
The coordination behaviour of a series of pyridyl azamacrocyclic ligands, some of them containing cyanomethyl and cyanoethyl pendant-arms, towards Mn(II) ion was studied. All the complexes were characterized by microanalysis, LSI mass spectrometry, IR, UV-Vis spectroscopy and magnetic measurements. Crystal structures of [MnL1][MnBr4] (1), [MnL3][MnBr4] · 2CH3CN (3), [Mn2L5Br4] · 2CH3CN (5) and [Mn2L6Br4] (6) complexes have been determined. The X-ray studies show the presence of an ionic mixed octahedral-tetrahedral complex for 1 and 2, with the manganese ion of the cation complex, endomacrocyclicly coordinated by the six nitrogen donor atoms from the macrocyclic backbone in a distorted octahedral geometry. Instead, the complexes 5 and 6 are dinuclear, and both manganese ions are coordinated by one pyridinic and two amine nitrogen atoms from the macrocyclic backbone and two bromide ions, being the geometry around the metal better described as distorted square pyramidal. In all cases, the nitrile pendant-arms do not show coordination to the metal ion.  相似文献   

12.
The reaction of Cu(ClO4)2·6H2O and Cd(ClO4)2 with di-(2-picolyl)sulfur (dps) leads to the formation of mononuclear complexes [Cu(dps)(H2O)(ClO4)](ClO4) (1) and [Cd(dps)2](ClO4)2 (2). The crystal structure of 1 exhibits a distorted square pyramidal geometry, coordinated by one sulfur and two nitrogen atoms from the dps ligand, one water molecule and one perchlorate oxygen atom. For 2, the environment around cadmium atom is in a distorted octahedron with four nitrogen and two sulfur atoms from the dps ligand. Cyclic voltammetric data show that complexes undergo two waves of a one-electron transfer corresponding to M(II)/M(III) and M(II)/M(I) processes. Spectral and electrochemical behaviors of the complexes are also discussed.  相似文献   

13.
The new zinc ternary complexes [Zn(cyclen)NO3]ClO4 (I), [Zn2(cyclen)2(m-nic)](ClO4)3 (II), [Zn2(cyclen)2(m-pic)](ClO4)3 (III) (cyclen=1,4,7,10-tetraazacyclododecane; nic=nicotinic acid; pic=picolinic acid) were synthesized and their spectral and thermal properties were investigated. The compounds were characterized by elemental analysis, IR spectroscopy and TG/DTG, DTA methods. Moreover, the way of coordination of pyridinecarboxylate anions was proposed on the basis of the spectral data and consequently proved with results of X-ray structure analysis. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

14.
Five novel nickel(II) complexes have been successfully synthesized with a heterocyclic ligand, Opdac, [Ni(Opdac)2]Cl2 (1), [Ni(Opdac)2(CH3OH)2]Br2(CH3OH)2 (2), [Ni(Opdac)2]I2 (3), [Ni(Opdac)2NO3]NO3 (4) and [Ni(Opdac)2ClO4]ClO4 (5) where Opdac = 4-(1-H-1,3-benzimidazole-2-yl)-1,5-dimethyl-2-phenyl-1-2-dihydro-3-H-pyrazol-3-one. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, magnetic susceptibility measurements, spectroscopic studies and TG/DTA methods. In all the complexes, Opdac acts as a bidentate ligand coordinating to Ni(II) ion via the benzimidazole imine nitrogen and the pyrazolone oxygen atoms. The complexes 1 and 3 have a tetrahedral geometry while 2, 4 and 5 have an octahedral geometry around the Ni(II) center.  相似文献   

15.
Varying coordination modes of the Schiff base ligand H2L [5-methyl-1-H-pyrazole-3-carboxylic acid (1-pyridin-2-yl-ethylidene)-hydrazide] towards different metal centers are reported with the syntheses and characterization of four mononuclear Mn(II), Co(II), Cd(II) and Zn(II) complexes, [Mn(H2L)(H2O)2](ClO4)2(MeOH) (1), [Co(H2L)(NCS)2] (2), [Cd(H2L)(H2O)2](ClO4)2 (3) and [Zn(H2L)(H2O)2](ClO4)2 (4), and a binuclear Cu(II) complex, [Cu2(L)2](ClO4)2 (5). In the complexes 1-4 the neutral ligand serves as a 3N,2O donor where the pyridine ring N, two azomethine N and two carbohydrazine oxygen atoms are coordinatively active, leaving the pyrazole-N atoms inactive. In the case of complex 5, each ligand molecule behaves as a 4N,O donor utilizing the pyridine N, one azomethine N, the nitrogen atom proximal to the azomethine of the remaining pendant arm and one pyrazole-N atom to one metal center and the carbohydrazide oxygen atom to the second metal center. The complexes 1-4 are pentagonal bipyramidal in geometry. In each case, the ligand molecule spans the equatorial plane while the apical positions are occupied by water molecules in 1, 3 and 4 and two N bonded thiocyanate ions in 2. In complex 5, the two Cu(II) centers have almost square pyramidal geometry (τ = 0.05 for Cu1 and 0.013 for Cu2). Four N atoms from a ligand molecule form the basal plane and the carbohydrazide oxygen atom of a second ligand molecule sits in the apex of the square pyramid. All the complexes have been X-ray crystallographically characterized. The Zn(II) and Cd(II) complexes show considerable fluorescence emission while the remaining complexes and the ligand molecule are fluorescent silent.  相似文献   

16.
The oxalato-bridged dinickel(II) complex with the title ligand, [Ni2(L a H)2(μ-ox)](ClO4)2·2H2O (1), was prepared and its structure was determined by X-ray crystallography, as well as that of the monomeric nickel(II) complex, [Ni(L a H)ox]ClO4·3H2O (2). In Complexes 1 and 2, the ligand, L a , is folded along the N(4)–Ni(1)–N(11) axis. The antiferromagnetic coupling between the two nickel(II) centers in 1 was revealed and the coupling constant, J?=??17.4?cm?1, and g?=?2.11 were estimated. It was found that the oxalato-bridged dimer 1 was readily converted to the mononuclear cis-nickel(II) complex [NiL a (OH2)](ClO4)2 (3a), in basic aqueous solution. In [NiL a (CH3CN)]I2 (3b), which was derived from 3a, the aminomethyl pendant arm is coordinated to the Ni(II) ion and L a is folded along the N(1)–Ni(1)–N(8) axis.  相似文献   

17.

This paper reports the synthesis, crystal structure and properties of two new mononuclear nickel(II) complexes, [NiL(phen)][ClO4]2(1) and [NiL(bpy)][ClO4]2(2), where L is bis(benzimidazol-2-ylmetheyl)(2-hydroxyethyl)amine and phen and bpy are 1,10-phenanthroline and 2,2'-bipyridine, respectively. The crystal structure of 1 ·2EtOH has been determined by single-crystal X-ray analysis. It crystallizes in the monoclinic system, space group C2/c, a= 24.279(2), b= 20.864(2), c= 17.635(1)Å, g = 121.730(2)°, Z= 8, R 1= 0.064, wR 2= 0.167. The Ni(II) ion in 1 ·2EtOH is coordinated to three nitrogen atoms and one oxygen atom of the ligand L and two nitrogen atoms of phen to form a distorted octahedron. Spectroscopic properties of 1 and 2 are reported.  相似文献   

18.
We reported the synthesis of tris(pyridyl)phosphine selenide (TppSe) and tris(4-methylpyridin-2-yl)phosphine selenide (MeTppSe), which were prepared by a simple and straightforward one-pot method with red phosphorus in a KOH/DMSO suspension, and treatment of resulted phosphines with selenium in hot toluene. These compounds were characterized by mass spectroscopy, 1H, 13C and 31P NMR spectroscopies and the structure of MeTppSe was characterised by a single-crystal X-ray diffraction. Furthermore, The reactions of selenides with Fe(ClO4)2·6H2O afforded two new iron(II) mononuclear metal complexes [Fe(TppSe)2][ClO4]2·3DMF (1) and [Fe(MeTppSe)2][ClO4]2·2DMF (2). Detailed structural analyses and magnetic susceptibility measurements confirm no spin transition from low-spin to the high-spin state between 2 and 300 K in two iron(II) complexes.  相似文献   

19.
New bi- and trihomonuclear Mn(II), Co(II), Ni(II), and Zn(II) complexes with sulfa-guanidine Schiff bases have been synthesized for potential chemotherapeutic use. The complexes are characterized using elemental and thermal (TGA) analyses, mass spectra (MS), molar conductance, IR, 1H-NMR, UV-Vis, and electron spin resonance (ESR) spectra as well as magnetic moment measurements. The low molar conductance values denote non-electrolytes. The thermal behavior of these chelates shows that the hydrated complexes lose water of hydration in the first step followed by loss of coordinated water followed immediately by decomposition of the anions and ligands in subsequent steps. IR and 1H-NMR data reveal that ligands are coordinated to the metal ions by two or three bidentate centers via the enol form of the carbonyl C=O group, enolic sulfonamide S(O)OH, and the nitrogen of azomethine. The UV-Vis and ESR spectra as well as magnetic moment data reveal that formation of octahedral [Mn2L1(AcO)2(H2O)6] (1), [Co2(L1)2(H2O)8] (2), [Ni2L1(AcO)2(H2O)6] (3), [Mn3L2(AcO)3(H2O)9] (5), [Co3L2(AcO)3(H2O)9] · 4H2O (6), [Ni3L2(AcO)3(H2O)9] · 7H2O (7), [Mn3L3(AcO)3(H2O)6] (9), [Co2(HL3)2(H2O)8] · 4H2O (10), [Ni3L3(AcO)3(H2O)9] (11), [Mn3L4(AcO)3(H2O)9] · H2O (13), [Co2(HL4)2(H2O)8] · 5H2O (14), and [Ni3L4(AcO)3(H2O)9] (15) while [Zn2L1(AcO)2(H2O)2] (4), [Zn3L2(AcO)3(H2O)3] · 2H2O (8), [Zn3L3(AcO)3(H2O)3] · 3H2O (12), and [Zn3L4(AcO)3(H2O)3] · 2H2O (16) are tetrahedral. The electron spray ionization (ESI) MS of the complexes showed isotope ion peaks of [M]+ and fragments supporting the formulation.  相似文献   

20.
Two pyrazole-based polydentate ligands, 1,3-bis(5-methyl-3-phenylpyrazol-1-yl)-propan-2-ol (Hmppzpo) and 1,3-bis(5-methyl-3-p-isopropylphenylpyrazol-1-yl)-propan-2-ol (Hmcpzpo), have been synthesized. A third ligand, 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-2-ol (Hdmpzpo), has been synthetically modified. Seven new M(II) coordination compounds of general formula M2L2X2 (M?=?Zn, Ni; X?=?NO3 or ClO4; L?=?dmpzpo, mppzpo or mcpzpo) or MLX (M?=?Pd; L?=?dmpzpo; X?=?Cl) were synthesized and structurally characterized by elemental analysis and FT-IR analysis. The crystal structures of [Zn2(μ-dmpzpo-O,N,N′)2(NO3)2]?·?2H2O (1?·?2H2O), [Ni2(μ-dmpzpo-O,N,N′)2(CH3CN)2](ClO4)2 (2) and Pd(μ-dmpzpo-N,N′)Cl2 (4) were determined by single-crystal X-ray crystallography. The crystal structures show that complexes 1?·?2H2O and 2 are center-symmetric dinuclear compounds, with two metal ions bridged by two alkoxo groups and each metal ion with a distorted square-pyramidal environment. The palladium complex, 4, displayed square-planar coordination geometry around the Pd(II) ion with trans arrangement.  相似文献   

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