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1.
Four new ligands, (4-methyl-phenyl)-pyridin-2-ylmethylene-amine (A), (2,3-dimethyl-phenyl)-pyridin-2-ylmethylene-amine (B), (2,4-dimethyl-phenyl)-pyridin-2-ylmethylene-amine (C) and (2,5-dimethyl-phenyl)-pyridin-2-ylmethylene-amine (D), and their corresponding copper(I) complexes, [Cu(A)2]ClO4 (1a), [Cu(B)2]ClO4 (1b), [Cu(C)2]ClO4 (1c), [Cu(D)2]ClO4 (1d), [Cu(A)(PPh3)2]ClO4 (2a), [Cu(B)(PPh3)2]ClO4 (2b), [Cu(C)(PPh3)2]ClO4 (2c) and [Cu(D)(PPh3)2]ClO4 (2d), have been synthesized and characterized by CHN analyses, 1H and 13C NMR, IR and UV–Vis spectroscopy. The crystal structures of [Cu(B)2]ClO4 (1b), [Cu(C)2]ClO4 (1c) and [Cu(A)(PPh3)2]ClO4 · 1/2CH3CN (2a) were determined from single crystal X-ray diffraction. The coordination polyhedron about the copper(I) center in the three complexes is best described as a distorted tetrahedron. A quasireversible redox behavior is observed for the complexes.  相似文献   

2.
6-Aminocoumarin reacts with pyridine-2-carboxaldehyde and has synthesized N-[(2-pyridyl)methyliden]-6-coumarin (L). The ligand, L, reacts with [Cu(MeCN)4]ClO4/AgNO3 to synthesize Cu(I) and Ag(I) complexes of formulae, [Cu(L)2]ClO4 and [Ag(L)2]NO3, respectively. While similar reaction in the presence of PPh3 has isolated [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3. All these compounds are characterized by FTIR, UV-Vis and 1H NMR spectroscopic data. In case of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3, the structures have been confirmed by X-ray crystallography. The structure of the complexes are distorted tetrahedral in which L coordinates in a N,N′ bidentate fashion and other two coordination sites are occupied by PPh3. The ligand and the complexes are fluorescent and the fluorescence quantum yields of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3 are higher than [Cu(L)2]ClO4 and [Ag(L)2]NO3. Cu(I) complexes show Cu(II)/Cu(I) quasireversible redox couple while Ag(I) complexes exhibit deposition of Ag(0) on the electrode surface during cyclic voltammetric experiments. gaussian 03 computations of representative complexes have been used to determine the composition and energy of molecular levels. An attempt has been made to explain solution spectra and redox properties of the complexes.  相似文献   

3.
Protonation of the bioactive ligand-antipyrine (AP, 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) has been considered, the crystal packing specific features for the protonated antipyrine perchlorate compounds ([APH]ClO4 · H2O (1, 2) and [AP2H]ClO4 (3, 4)), as well as the crystal structure particularities for [Tm(AP)6](ClO4)3 (5) and [Yb(AP)6](ClO4)3 (6) have been elucidated. The protonation ability—complex formation ability relationship has been revealed for a number of organic ligands. Quantum-chemical calculations (DFT) and comparison with the experimental data allowed aligning some organic ligands in a row according to their ability to be protonated and to be incorporated into the inner coordination sphere of the complex.  相似文献   

4.
Abstract

Two mononuclear heteroleptic copper complexes, [Cu(±trans-dach)(bpy)](ClO4)2 1a and [Cu(±trans-dach)(phen)](ClO4)2 2a [dach?=?1,2-diaminocyclohexane, bpy?=?2,2′-bipyridine and phen?=?1,10-phenanthroline], were synthesized and analyzed by CHN analysis, electronic absorption, FT-IR spectroscopy, EPR, and SXRD. The molecular structures of 1a and 2a showed octahedral geometry around Cu(II). Both complexes interacted with phosphoesters and DNA. Their binding affinities with diphenylphosphate, di n-butylphosphate, trimethylphosphate, and triphenylphosphate were studied by UV–vis spectroscopy. For understanding the stereochemical role of dach ligand toward DNA interaction, enantiopure DACH complexes [Cu(R,R-trans-dach(bpy)](ClO4)2 1b, [Cu(S,S-trans-dach)(bpy)](ClO4)2 1c, [Cu(cis-dach)(bpy)](ClO4)2 1d, [Cu(R,R-trans-dach)(phen)](ClO4)2 2b, [Cu(S,S-trans-dach)(phen)](ClO4)2 2c, and [Cu(cis-dach)(phen)](ClO4)2 2d were synthesized and analyzed. All complexes interacted with calf thymus-DNA (CT-DNA) as studied by UV–vis spectroscopy. The nature of binding to CT-DNA was groove/electrostatic as supported by circular dichroism, cyclic voltammetry, and docking studies. Complexes were able to cleave plasmid DNA at 12.5 µM (1ad) and 6 µM (2ad), where 2d showed 64% Form II and 36% Form III. The in vitro cytotoxic studies of two different cancer cell lines showed inhibition with low IC50 value in comparison to reference control (cisplatin). These complexes are efficient in inducing apoptosis in cancer cells, making them viable for potent anticancer activity.  相似文献   

5.
Two copper(II) complexes, [Cu(L)2](ClO4)2] and [Cu(L)(bipy)](ClO4)2, were prepared and characterized by the spectroscopic and analytic methods, where L is N-butylbenzimidazole and bipy is 2,2′-bipyridine. Single crystals of [Cu(L)(bipy)](ClO4)2 suitable for X-ray diffraction study were obtained by slow diffusion of diethyl ether into a DMF solution of the complex and the complex was found to crystallize as [Cu(L)(bipy)](ClO4)2·DMF. The asymmetric unit contains one [Cu(L)(bipy)]2+, two uncoordinated perchlorates, and one DMF solvate. Coordination geometry around Cu(II) is distorted square pyramidal with τ value of 0.31. Thermal properties of the complexes were examined by thermogravimetric analysis, indicating that the complexes are thermally stable to 310?°C. The metal complexes were screened for their in vitro antibacterial and antifungal activities Bacillus subtilis and Bacillus cereus (as Gram(+) bacteria), Escherichia coli, Enterobacter aerogenes, and Klebsiella pneumoniae (as Gram(–) bacteria), and Saccharomyces cerevisiae, Candida utilis, and Candida albicans (as yeasts). The complexes show antibacterial and antifungal activities against bacteria and yeasts.  相似文献   

6.
Li  Baolong  Xu  Zheng  Cao  Zhengbai  Zhu  Liming  Yu  Kaibei 《Transition Metal Chemistry》1999,24(6):622-627
The reaction of diethylenetriamine (dien) and 1,2-bis(1,2,4-triazole-1-yl)ethane (btrz) with Cu(ClO4) · 6H2O forms [Cu(dien)(btrz)(ClO4)2] (1), and the reaction of [Cu(en)2(ClO4)2] (en = ethylenediamine) with btrz forms [Cu(en)2(btrz)(ClO4)2] (2). Complexes (1) and (2) were characterized by elemental analysis, i.r., electronic spectroscopy, e.s.r. and magnetic susceptibility. Their crystal structure was determined by X-ray diffraction. In complex (1), Cu is coordinated by a dien and two btrz, forming a distorted CuN5 square pyramid with one btrz bound at the apical position. In complex (2), Cu is coordinated by two en and two nitrogen atoms of btrz forming an elongated octahedron. Both complexes have a one-dimensional chain structure in which btrz ligands bridge between pairs of Cu atom.  相似文献   

7.
Several new copper(I) complexes of a group of bidentate bithiazole ligands have been isolated. The compounds prepared are bis(2,2′-dimethyl-4,4′-bithiazole)copper(I) perchlorate ([Cu(me-b)2]ClO4), bis(4,4′-dimethyl-2,2′-bithiazole)copper(I) perchlorate ([Cu(me-i)2]ClO4), bis(2,2′-diphenyl-4,4′-bithiazole) copper(I) perchlorate ([Cu(ph-b)2]ClO4), bis(4,4′-diphenyl-2,2′-bithiazole)copper(I) perchlorate ([Cu(ph-i)2]ClO4), bis(4,4′,5,5′-tetraphenyl-2,2′-bithiazole)-copper(I) perchlorate ([Cu(ph4-i)2]ClO4, bis(2,2′-bithiazole)copper(l) perchlorate ([Cu(i)2]CIO4), 2,2′-bithiazolecopper(I) perchlorate ([Cu(i)ClO4), (2,2′-bithiazole)bis(triphenylphosphinesulfide)copper(I) perchlorate ([Cu(i)(SPph3)2]ClO4,(2,2′-bithiazole)bis-( triphenylphosphine)copper(I) perchlorate ([Cu(i)(Pph3)2]ClO4), and (4,4′-bithiazole)bis(triphenylphosphine) copper(I) perchlorate ([Cu(b)(Pph3)2]ClO4). Several synthetic techniques were required including one developed in this work which involved the conversion of [Cu(Pph3)4]ClO4 into the thiophosphine complex by reaction with sulfur and subsequent use of this as a labile precursor complex. Optical spectra of the complexes indicate extensive solution dissociation. Several of the complexes ([Cu(ph-b)2]ClO4, [Cu(ph-i)2]CIO4, and [Cu(i)(Pph3]ClO4) were photoluminescent in the solid; one ([Cu(ph-b)2]ClO4) showed extensive loss of emission during irradiation. Most of the complexes prepared here appear to bind through the thiazole nitrogen atoms. However, infrared evidence suggests that in two of the complexes thiazole sulfur atoms participate in the bonding.  相似文献   

8.
以三氨乙基胺和N-甲基咪唑醛为原料合成了三角架多咪唑配体((min)3tren),并合成了五个过渡金属配合物:[Zn(min)3tren](ClO4)21, [Cu(min)3tren](ClO4)22, [Ni(min)3tren](ClO4)23, [Co(min)3tren](ClO4)24, and [Mn(min)3tren](ClO4)2CH3CN 5,通过元素分析,摩尔电导率,红外和电子光谱确定了化合物的组成。对配合物4和5进行了晶体结构测定。结果表明,在这两个化合物中金属原子均处于扭曲的八面体配位环境,分别与三个亚胺氮原子和三个咪唑氮原子配位。配合物4和5的电化学研究表明在乙腈溶液中,有[Co-O2]n-和[Mn-O2]n-存在,认为4和5是很好的超氧化物清除剂。  相似文献   

9.
Six mononuclear complexes are reported with the tetradentate ligand N,N′-bis(2-pyridylmethyl)-1,3-propanediamine, (abbreviated as pypn) i.e. [Cu(pypn)(ClO4)2](H2O)1/2 (1), [Fe(pypn)Cl2](NO3) (2), [Zn(pypn)Cl](ClO4) (3), [Co(pypn)(NCS)2](ClO4) (4), [Co(pypn)(N3)2](ClO4) (5), [Zn(pypn)(NCS)2] (6). The synthesis and X-ray crystal structures of all six compounds and their spectroscopic properties are presented.The geometry of the Cu2+, Co3+, Zn2+, Fe3+ ions is essentially octahedrally based, with the mm conformation (for Cu) and msf conformations for the other 3 metal ions; in compound 3 the geometry around the Zn2+ is distorted trigonal bipyramidal. The stabilisation of the crystal lattices is maintained by interesting, relative strong hydrogen bonds.  相似文献   

10.
The chemistry of first row transition metal complexes obtained from the ligand dipyrido[3,2-f:2′,3′-h]-quinoxaline (dpq) have been reported. The reaction between Cu(ClO4)2 · 6H2O with dpq under different reaction conditions led to the isolation of three polymorphic copper(II) complexes [Cu(dpq)2(H2O)](ClO4)2 · H2O (2), [Cu(dpq)2(ClO4)](ClO4) (3) and [{Cu(dpq)2(H2O)}{Cu(dpq)2(ClO4)}](ClO4)3 (4). The bluish-green compound 2, obtained by reacting Cu(ClO4)2 · 6H2O with dpq in methanol, has a distorted trigonal bipyramidal structure with τ = 0.55. The reaction between Cu(ClO4)2 · 6H2O and dpq in dry acetonitrile produced the blue compound 3 in which the copper(II) centre has a distorted square planar geometry. When the condensation reaction between 1,10-phenanthroline-5,6-dione and 1,2-diaminoethane was carried out in the presence of Cu(ClO4)2 · 6H2O in methanol, the green copper(II) complex 4 was isolated along with 1. The structure determination of 4 has established the presence of two different complex cations in the asymmetric unit and they are considered as co-crystals. In the zinc(II) compound [Zn(dpq)2(ClO4)2] (5), the two perchlorates are unidentately coordinated to the metal centre, providing a distorted octahedral geometry. The quinoxaline ring in 5 is involved in intermolecular π–π interactions, leading to the generation of a sinusoidal chain. The proton NMR spectra, especially those of the paramagnetic complexes [Ni(dpq)3](ClO4)2 (6) and [Co(dpq)3](ClO4)2 (7), have been studied in detail. The electronic absorption spectra and the redox behaviour of the copper(I), copper(II), cobalt(II) and cobalt(III) complexes have been studied. The three copper(II) compounds 24 show identical absorption spectra and redox properties when measured in acetonitrile, although in nitromethane they show small but definite differences in their spectral and redox features.  相似文献   

11.
Twelve oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes Ln[Cu(PMoxd)]4(ClO4)3 · 5H2O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and PMoxd = the N,N′-Bi(α-pyridylmethyl)-oxamide dianion) and 12 oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes with the formula of Ln[Cu(PEoxd)]4(ClO4)3 · 5H2O (PEoxd = the N,N′-Bi(α-pyridylethyl)-oxamide dianion) were synthesized and characterized. The magnetic properties of Gd[Cu(PMoxd)]4(ClO4)3 · 5H2O (7) and Gd[Cu(PEoxd)]4(ClO4)3 · 2H2O (19) show that there are ferromagnetic interactions between Gd(III) and Cu(II) in the complexes with J Cu–Gd = 1.38 cm?1 and J Cu–Gd = 1.00 cm?1, respectively. Fluorescent quenching phenomena for Eu[Cu(PMoxd)]4(ClO4)3 · 5H2O (6) and Tb[Cu(PMoxd)]4(ClO4)3 · 5H2O (8) were also observed.  相似文献   

12.
Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO3)2, Cu(ClO4)2, Zn(ClO4)2, Ni(NO3)2 and PdCl2 gives complexes with stoichiometry [Cu(L)2(H2O)2](NO3)2, [Cu(L)2(H2O)2](ClO4)2, [Zn(L)2(H2O)2] (ClO4)2, [Ni(L)2(H2O)Cl](NO3) and PdLCl2. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)2(H2O)2](NO3)2, [Cu(L)2(H2O)2](ClO4)2, and [Zn(L)2(H2O)2](ClO4)2 were determined by X-ray crystallography. The cation complexes [M(L)2(H2O)2] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.  相似文献   

13.
Two copper(II) complexes of disubstituted 2,2′-bipyridine (bpy = 2, 2′-bipyridine) with tetraalkylammonium groups, [Cu(L1)2Br](ClO4)5·2H2O (1) and [Cu(L2)2Br](ClO4)5·H2O (2) (L1 = [4, 4′-(Et3NCH2)2-bpy]2+, L2 = [4, 4′-((n-Bu)3NCH2)2-bpy]2+), have been synthesized and characterized. X-ray crystallographic study of 1 indicates that Cu(II) is a distorted trigonal bipyramidal or square pyramid. DNA binding of both complexes was studied by UV spectroscopic titration. In the presence of reducing reagents, the cleavage of plasmid pBR322 DNA mediated by both complexes was investigated and efficient oxidative cleavage of DNA was observed. Mechanistic study with reactive oxygen scavengers indicates that hydrogen peroxide and singlet oxygen participate in DNA cleavage.  相似文献   

14.
高氯酸诺氟沙星铜(Ⅱ)(英)   总被引:3,自引:0,他引:3  
0CommentExtensiveinvestigationshavebeendoneaboutthesupramolecularchemistryofmetalionswithNor-floxacin(H-Norf,1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinolinecarboxylicacid)sincemanyorganiccompoundsusedinmedicinedonothaveapurelyorganicmodeofaction;someareacti-vatedorbiotransformedbymetalions,othershavedi-rectorindirecteffectonthemetalionmetabolism[1~5].ThereactionofCu(ClO4)2·6H2OwithH-Norfunderhydrothermalconditionsgivesamonomericcomplex[Cu(H-Norf)2](ClO4)2(1)inwhichCu髤i…  相似文献   

15.
Three novel copper(II) complex [Cu2(bpa)(μ‐PhCO2)](ClO4)2 ( 1 ), [Cu2(bpa) (μ‐pyz)](ClO4)2 ( 2 ), and [Cu(Hbpa)](ClO4)2·2CH3CN ( 3 ) have been synthesized by the reaction of Hbpa with Cu(ClO4)2·6H2O in the presence and absence of exogenous ligands (where Hbpa = N, N'‐bis(picolinidene‐N‐oxide)‐2‐hydroxy‐1, 3‐diamino‐propane). Molecular structures of these compounds have been elucidated by single crystal X‐ray diffraction. 1 and 2 are both binuclear complexes in which two copper atoms are linked by the endogenous alkoxide oxygen and the exogenous benzoate and pyrazolate ligands, respectively. 3 consists of a one‐dimensional polymeric structure, in which Hbpa functions as a bridging mode.  相似文献   

16.
Two coordination polymers, [Cu(bpp)(H2O)2(ClO4)2]n (1) and {[Cu(bpds)2(ClO4)2] · 1.5(H2O)}n (2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,4′-bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement. Both the coordination polymers display 1D chains with perchlorate anions acting as pendant ligands. In 1 undulated polymers are built by Cu(H2O)2(ClO4)2 units connected by single bpp and in complex 2 Cu(ClO4)2 fragments are linked by pairs of bpds ligands to form a double-stranded chain. The crystal packing evidences polymers of 1 involved in weak H-bonding interactions leading to a 3D supramolecular network. Magnetic study reveals weak antiferromagnetic interactions in both complexes.  相似文献   

17.
New oxamido-bridged binuclear CuII-CuII complexes, [Cu(Oxen)Cu(Bipy)2](ClO4)2 (I) and [Cu(Oxen)Cu(4,4??-Bipy)2(H2O)2](ClO4)2 (II) (Oxen is N,N??-bis(2-aminoethyl)oxamide dianion, Bipy = 2,2??-bipyridine, 4,4??-Bipy = 4,4??-bipyridine), have been constructed and structurally characterized by X-ray crystallography. In these two complexes, each Cu2+ ion is located in a slightly distorted square-pyramidal environment. Complex I is extended to two-dimensional by face-to-face ??-??-stacking with a distance of 3.648 II is raised to one-dimensional by face-to-face ??-??-stacking and intermolecular H-bonding interaction with distances of 3.651 and 2.767 I is also investigated.  相似文献   

18.
Modification of Layer Silicates by Sterically Demanding Metal Complexes: Synthesis and Intercalation of the Square Planar Complexes [Cu(bppep)(H2O)](ClO4)2 and [Ni(bppep)(Cl)]Cl (bppep = 2,6-Bis[1-phenyl-1-(pyridine-2-yl)ethyl]pyridine) in Hectorite Sodium-aqua hectorite reacts with [Cu(bppep)(H2O)](ClO4)2 and [Ni(bppep)(Cl)]Cl with exchange of the sodium-aqua cations against the complex cations [Cu(bppep)(H2O)]2+ and [Ni(bppep)(Cl)]+, respectively. In addition, cation-anion pairs of [Cu(bppep)(H2O)](ClO4)2 and [Ni(bppep)(Cl)]Cl are also intercalated between the hectorite layers (intersalation). On the other hand, it is possible to synthesize [Cu(bppep)(H2O)]2+ or [Ni(bppep)(H2O)]2+ modified hectorites without additional ion-pair intercalation (intersalation) by reaction of nickel- and copper-hectorites with the bppep ligand.  相似文献   

19.
Hydrothermal reactions of ciprofloxacin with Cu(ClO4)2?·?6H2O, and ofloxacin with Cu(CH3COO)2?·?4H2O, yield two metal complexes: [Cu(H-Cip)2]?·?(ClO4)2?·?6H2O (1) and [Cu(Ofl)2?·?H2O]?·?2H2O (2), which were characterized by elemental analysis, IR and single crystal diffraction analyses. Compounds 1 and 2 were screened for antibacterial activities against Staphylococcus aureus, Escherichia coli, Candida albicans and pseudomonas aeruginosa.  相似文献   

20.
Cd(ΙΙ) and Cu(II) complexes of an acyclic pentadentate Schiff base were prepared by template condensation of two equivalents of 2-acetylpyridine with one equivalent of bis(3-aminopropyl)amine in methanol. The resulting complexes [CdL(NO3)]ClO4 (1) and [CuL](ClO4)2 · CH3CN (2) were characterized by X-ray crystallography, elemental analysis, IR and mass spectrometry in both cases and by NMR in the case of 1. The X-ray crystallographic structure determination of these complexes revealed six-coordinate distorted octahedral geometry for 1, with the sixth coordination by nitrate and five-coordinate for 2 with trigonal-bipyramidal Cu(II).  相似文献   

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