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1.
Copper(I)/(II) complexes with the ligand 2-aminoethyl(2-pyridylmethyl)1,2-ethanediamine (apme, abbreviated as PDT in the literature as well) were prepared and characterized. Crystal structures of the copper(I) complexes, [Cu2(apme)2]X2 (1, 2; X = ClO4, CF3SO3), showed that they are dinuclear, in contrast to the trigonal bipyramidal copper(II) complexes [Cu(apme)Cl]BPh4 (3) and [Cu(apme)(DMF)](BPh4)2 (4). 1 and 2 could be investigated in solution by NMR spectroscopy and 3 and 4 by cyclovoltammetry. From the results of these studies it is clear that in solution equilibria between the dinuclear complexes 1/2 and another species exist, most likely the monomeric [Cu(apme)CH3CN]+. Time-resolved UV/vis spectra at low temperatures allowed the spectroscopic detection of dioxygen adduct complexes as reactive intermediates during the oxidation of 1/2 with dioxygen that seem to play an important role in copper enzymes such as peptidylglycine--hydroxylating monooxygenase (PHM).  相似文献   

2.
The new tripodal phosphine CH3C{CH2P(m-CF3C6H4)2}3, CF3PPP, was prepared by reacting CH3C(CH2Br)3 with Li+P(m-CF3C6H4)2, the latter being best obtained by adding Li+NiPr2 to PH(m-CF3C6H4)2. The rhodium complexes [RhCl(CO)(CF3PPP)], [Rh(LL)(CF3PPP)](CF3SO3) (LL = 2 CO or NBD), [RhX3(CF3PPP)], [RhX(MeCN)3(CF3PPP)](CF3SO3)2 (X = H and Cl), [RhCl2(MeCN)(CF3PPP)](CF3SO3) and [Rh(MeCN)3(CF3PPP)](CF3SO3)3 were prepared and characterized. The X-ray crystal structure of [Rh(NBD)(CF3PPP)](CF3SO3) is reported. The lower oxygen sensitivity of the CF3PPP rhodium(I) complexes, relative to the corresponding species with the parent ligand CH3C(CH2PPh2)3, is attributed to the higher effective nuclear charge on the metal centers caused by the presence of the six CF3 substituents on the terdentate phosphine. A similar effect may be responsible for the easier hydrolysis of the CF3PPP-containing, cationic rhodium(III) complexes relative to the corresponding compounds of the parent ligand.  相似文献   

3.
The preparation of N-, S- and O-donor ligand adducts with CuX+(HX=6-methyl-2-formylpyridinethiosemicarbazone (6HL); 2-formylpyridine-2-methylthiosemicarbazone (2′L); 2-formylpyridine-4′-methylthiosemicarbazone (4′HL)) is described. The N-donors, 2,2′-bipyridyl (bipy), 4-dimethylaminopyridine (dmap) give the complexes [Cu(6L)(bipy)]PF6, [Cu(6L)(bipy)]Cl·5H2O, [Cu(4′L)(bipy)]PF6, [Cu(6L)(dmap)2]PF6·2.5 H2O and [Cu(4′L)(dmap)2]PF6·H2O which have been characterized by physical and spectroscopic techniques. Pentafluorothiophenolate (pftp) gives S-donor complexes [CuX(pftp)] (X=6L and 4′L) and thiolato co-ordination is proposed on the basis of spectroscopic evidence. Paratritylphenolate (ptp) and HPO2−4 give O-donor complexes [Cu(6L)(ptp)], [Cu(4′L)(ptp)], [{Cu(6L)}2HPO4]·4H2O, and [{Cu(4L)}2HPO4]·5H2O which have been characterized by physical and spectroscopic techniques, as have the precursor complexes [Cu(6L)(CH3COO)]·H2O, [Cu(4′L)(CH3COO)], Cu(6HL)(CF3COO)](CF3COO)·0.5H2O, [Cu(4′HL)(CF3COO)](CF3COO), [Cu(2′L)Cl2] and [Cu(2′L)(NO3)2]. Protonation constants for the ligands and some of their complexes have been determined. 2-Formylpyridinethiosemicarbazone (HL) complexes of silver, gold, zinc, mercury, cadmium and lead are also discussed. Cytotoxicity against the human tumor cell line HCT-8 and antiviral data for selected compounds are presented.  相似文献   

4.
Polynuclear S-bridged complexes of the general formula {[Co2L6]M}n+ with M = Co(III), Cd(II), Pb(II), Ni(II), Zn(II) and Hg(II) were prepared from [Co(2-aminoethanethiolate)3] and the appropriate metal salt. Proton and 13C NMR spectra are consistent with structures previously proposed for these species with 13C chemical shifts dependent on the bridging metal ion. Electrochemical studies are consistent with a model in which an S-bonded ML6 moiety (i.e., the bridging metal ion and the six aminoethanethiolate ligands) acts as a ‘dodecadentate’ ligand bonded to two Co3+ ions. Reduction of the terminal cobalt ions in these trinuclear complexes is observed in the range −0.75 to −1 V vs. SCE on mercury, gold or glassy carbon working electrodes. For complexes with relatively labile bridging ions, the electrode reaction is irreversible, presumably due to rapid decomposition of the labile cobalt(II) product. For the tricobalt(III) derivative, however, the electrode reaction is reversible consistent with other recent observations on cage or otherwise stereorestrictive ligand systems [1].  相似文献   

5.
《Inorganica chimica acta》1986,116(2):153-156
Complexes of Cu(II), Ni(II) and Co(II) with the Schiff base 1H-indole-3-ethylensalicylaldimine as ligand are studied. The isolated complexes correspond to the general formulae ML2 (where L= ligand).The complexes were characterized by mass spectra, IR, 1H NMR, UVVis spectra and magnetic measurements.The results indicated that the ligands coordinate through N and O with the metal ions in different stereochemistries.  相似文献   

6.
The Schiff base ligand, oxalic bis[(2-hydroxybenzylidene)hydrazide], H(2)L, and its Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes were prepared and tested as antibacterial agents. The Schiff base acts as a dibasic tetra- or hexadentate ligand with metal cations in molar ratio 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes, respectively. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, Mass, and UV-Visible spectra and the magnetic moments and electrical conductance of the complexes were also determined. For binuclear complexes, the magnetic moments are quite low compared to the calculated value for two metal ions complexes and this shows antiferromagnetic interactions between the two adjacent metal ions. The ligand and its metal complexes were tested against a Gram + ve bacteria (Staphylococcus aureus), a Gram -ve bacteria (Escherichia coli), and a fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.  相似文献   

7.
In this paper the oxygenation of HDTHCo homo and heterodinuclear complexes with Cu(II), Ni(II) and Pb(II) in aqueous solution by control of the stoichiometry of metal ions and HDTH as well as p[H] of solution was investigated (HDTH is a dinucleating 28-membered hexaazadiphenol macrocyclic ligand, 3,7,11,19,23,27-hexaaza-33,34-dihydroxy-15,31-dimethyl-tricyclo-tetratriaconta-1(32),13,15,17(34),29(33),30-hexaene). The pH potentiometric method was utilized successfully to determine oxygenation constants and to determine the distribution of species present in the solution as a function of p[H]. Spectrophotometry was used to investigate the oxygenation process of the homo and heterodinuclear complexes. The X-ray crystal structure of homodinuclear complexes of Ni(II) is also reported. These studies suggested autooxidation takes place during the oxygenation of homo and heterodinuclear Co(II) complexes of the macrocyclic ligand. The neighboring effect increases in the order Ni(II)<Cu(II)<Pb(II)<Co(II). Pb(II) stimulates the neighboring Co(II) to accept dioxygen in its sixth vacant position. Ni(II) is not helpful to Co(II) in its oxygenation.  相似文献   

8.
S(IV) (SO(2),HSO(3)(-)andSO(3)(2-)) autoxidation catalyzed by Cu(II)/tetraglycine complexes in the presence of DNA or 2'-deoxyguanosine (dGuo) resulted in DNA strand breaks and formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo), respectively. Ni(II), Co(II) or Mn(II) (1.0x10(-4)M) complexes had much smaller effects. Cu(II)/tetraglycine (1.0x10(-4)M) in the presence of Ni(II) or Mn(II) (10(-7)-10(-6)M) and S(IV) showed remarkable synergistic effect with these metal ions producing a higher yield of 8-oxodGuo. Oxidation of dGuo and DNA damage were attributed to oxysulfur radicals formed as intermediates in S(IV) autoxidation catalyzed by transition metal ions. SO*(3)(-) and HO* radicals were detected by EPR-spin trapping experiments with DMPO (5,5-dimethyl-1-pyrroline-N-oxide).  相似文献   

9.
Manganese tricarbonyl complexes (η5-C5H4CH2CH2Br)Mn(CO)3 (3) and (η5-C5H4CH2CH2I)Mn(CO)3 (4), with an alkyl halide side chain attached to the cyclopentadienyl ligand, were synthesized as possible precursors to chelated alkyl halide manganese complexes. Photolysis of 3 or 4 in toluene, hexane or acetone-d6 resulted in CO dissociation and intramolecular coordination of the alkyl halide to manganese to produce (η51-C5H4CH2CH2Br)Mn(CO)2 (5) and (η51-C5H4CH2CH2I)Mn(CO)2 (6). Low temperature NMR and IR spectroscopy established the structures of 5 and 6. Photolysis of 3 in a glass matrix at 91 K demonstrated CO release from manganese. Low temperature NMR spectroscopy established that the coordinated alkyl halide complexes are stable to approximately −20°C.  相似文献   

10.
The synthesis and characterization of a ferrocenyl-derived tridentate ligand, ferrocenyltris((methylthio)methyl)borate (FcTtP), and its representative metal complexes, [(FcTt)Cu]4 and [FcTt]2M (M = Fe, Co and Ni), are reported. The M = Fe complex exhibits spin-crossover behavior with a μeff = 1.19 μB at 25°C. The low-spin Co(II) derivative (1.88 μB) exhibits a characteristic axial electron paramagnetic resonance (EPR) spectrum, gav = 2.13, A = 53 G and A¦ = 43 G. The [FcTt]2M complexes display reversible two-electron redox processes assigned to ligand-centered events about 200 mV negative of the ferrocene-ferrocenium couple. [(FcTt)Cu]4 and [FcTt]2Ni have been characterized by X-ray diffraction. X-ray data for [(FcTt)Cu]4: monoclinic space group C2/c, with a = 24.3747(3) Å, b = 20.0857(2) Å, c = 17.2747(4) Å, β = 95.843(1)°, V = 8413.5(3) Å3, and Z = 4; [FcTt]2Ni: monoclinic space group C2/c, with a = 12.6220(3) Å, b = 11.6002(3) Å, c = 25.0125(7) Å, β = 94.067(1)°, V = 3653.1(2) Å3, and Z = 4.  相似文献   

11.
Three seriesof Rh(I) complexes of the type Tp3R,5RRh(LL), with LL = 2 CO (1), norbornadiene (NBD) (2) and 1,5-cyclooctadiene (COD) (3) and the tris (pyrazolyl)borate (Tp) ligands 3R=5R=Me (a), 3R=CF35R=Me (b); and 3R=5R=CF3 (c) were synthesized and fully characterized by IR and multinuclear NMR spectroscopy. Three isomeric forms were identified in solutions of these complexes: two square-planar isomers with a κ2-Tp3R,5R ligand, the uncoordinated pyrazolyl ring occupying either an equatorial position (type A), or an axial position (type B), and a five-coordinate species with a κ3, Tp3R,5R ligand (type C). In the carbonyl complexes 1 the dynamic equilibria between these isomers are solvent dependent. Interestingly, solutions of complex 1c contained all three isomers simultaneously. 103Rh and 13C NMR spectral studies indicate that the NBD compounds, 2, preferentially form square-planar complexes when TpCF3,Me and TpCF3,CF3 are present, while for the COD complexes, 3, square-planar complexes are preferred for all three Tp-type ligands. The X-ray structure of TpCF3,MeRh(CO)2 (1b) was determined (spacce group C2/ c,a = 21.271(9), B = 11.004(3), C = 21.563(9) Å, β = 114.93(3)°, V=4577(3) Å3, Z = 8, R = 3.41, Rw = 4.70). Its structure is of type B, with the third pyrazolyl ring axially placed, the N(4) being almost directly above the Rh atom but exerting only a weak Rh-N interaction.  相似文献   

12.
The Schiff base ligand, oxalic bis[(2-hydroxybenzylidene)hydrazide], H2L, and its Cu(II), Ni(II), Co(II), UO2(VI) and Fe(III) complexes were prepared and tested as antibacterial agents. The Schiff base acts as a dibasic tetra- or hexadentate ligand with metal cations in molar ratio 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes, respectively. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H NMR, Mass, and UV-Visible spectra and the magnetic moments and electrical conductance of the complexes were also determined. For binuclear complexes, the magnetic moments are quite low compared to the calculated value for two metal ions complexes and this shows antiferromagnetic interactions between the two adjacent metal ions. The ligand and its metal complexes were tested against a Gram + ve bacteria (Staphylococcus aureus), a Gram -ve bacteria (Escherichia coli), and a fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.  相似文献   

13.
Kefzol (kzl), a beta-lactam antibiotic, possesses various donor sites for interaction with transition metal(II) ions [Co(II), Cu(II), Ni(II) and Zn(II)] to form complexes of the type [M(kzl)2]Cl2 and [M(kzl)Cl], with molar ratio of metal: ligand (M:L) of 1:2 and 1:1 respectively. These complexes were prepared and characterized by physicochemical and spectroscopic methods. Their IR and NMR spectra suggest that kefzol potentially acts as a bidentate, tridentate as well as monoanionic tetradentate ligand. The complexes have been screened for antibacterial activity and results were compared with the activity of the uncomplexed antibiotic against Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Escherichia coli and Proteus mirabilis. The metal complexes were found to be more potent against one or more bacterial species than the uncomplexed kefzol.  相似文献   

14.
On the basis of electron spin resonance results, the 1:1 Cu(II), Co(II), Co(II)-O2, and Ni(III) complexes of bleomycin(BLM) have been compared with the corresponding metal complexes of its biosynthetic intermediate(P-3A). The present study suggests that (1) P-3A is an useful ligand for the clarification of metal-binding sites of BLM; (2) the secondary amine, pyrimidine ring nitrogen, deprotonated peptide nitrogen of histidine residue, and histidine imidazole groups as planar ligand donors, and the α-amino group as axial donor, are substantially important for metal-coordination of BLM; and (3) the sugar and bithiazole portions of BLM probably contribute to stabilization of Co(II)-O2 adduct complex and axial sixth coordination of Cu(II) and Ni(III) complexes.  相似文献   

15.
A new ligand N-salicyloyl-N'-o-hydroxythiobenzhydrazide (H2Sotbh) forms complexes [Mn(HSotbh)2], [Fe(Sotbh-H)(H2O)2], [M(Sotbh)] [M=Co(II), Cu(II) and Zn(II)] and [Ni(Sotbh)(H(2)O)2], which were characterized by various physico-chemical techniques. M?ssbauer spectrum of [Fe(Sotbh-H)(H2O)2] reveals the quantum admixture of 5/2 and 3/2 spin-states. Mn(II), Cu(II) and Ni(II) complexes were observed to inhibit the growth of tumor in vitro, whereas, Fe(III), Co(II), Zn(II) complexes did not. In vivo administration of Mn(II), Cu(II) and Ni(II) resulted in prolongation of survival of tumor bearing mice. Tumor bearing mice administered with Mn(II), Cu(II) and Ni(II) complexes showed reversal of tumor growth associated induction of apoptosis in lymphocytes. The paper discusses the possible mechanisms and therapeutic implication of the H2Sotbh and its metal complexes in tumor regression and tumor growth associated immunosuppression.  相似文献   

16.
The open-chain, potentially, pentadentate, ligan 1,11-bis(dimethylamino)-3,6,9-trimethyl-3,6,9,-triazaundecane (Me7tetren) forms a series of metal complexes having the general formula [M(Me7tetren)]Y2 (Y = 1, M = Co, Ni; Y = ClO4, M = Co, Ni, Cu, Zn). On the basis of their physical properties, it is suggested that all these compounds contains isostructural five-coordinate [M(Me7tetren)]2+ cations, the ligand acting as pentadentate. These complexes react in solution with thiocyanate ion to give mono- and, with exception of copper(II), di-thiocyanato five- and six-co-ordinate derivatives. Mono-thiocyanato derivatives of cobalt(II), nickel(II) and zinc(II) have been isolated as tetraphenylborate salts. Cobalt(II) and nickel (II) di-thiocyanato derivatives have been also isolated. Results are discussed in terms of the steric requirements of the ligand and electronic properties of the metal ions.  相似文献   

17.
The first 1:2 metal complexes of 2-(2′-pyridyl)quinoxaline (L) have been isolated. The physical and spectroscopic characteristics of the compounds [MCl2L2] (M = Ni, Cu, Cd) and [CuIL2](PF6) are described. The structure of the copper(I) complex has been determined by X-ray diffraction methods. Crystals are orthorhombic, space group Pcnb with A = 11.014(2), B = 12.886(2), C = 17.806(4) Å, V = 2527.1(9) Å3 and Z = 4. Refinement of the structure gave a final R factor of 0.046 (Rw = 0.041) for 814 unique reflections having I > 2.0σ(I). The ligand L acts as a bidentate chelate, the ligated atoms being the pyridine nitrogen and the nearest quinoxaline nitrogen. The structure of [CuL2]+ consists of a distorted tetrahedral arrangement around the copper(I) atom with Cu---N bond lengths of 2.023(6) and 2.059(5) Å and the N---Cu---N angle of the chelating ligand equal to 80.6(2)°. A monomeric trans pseudo-octahedral stereochemistry is assigned for the [MCl2L2] complexes.  相似文献   

18.
The Ru(III) metronidazole-maltolato and -ethylmaltolato complexes, trans-[RuL2(metro)2]CF3SO3 (L = ma (1a) or etma (1b)), have been synthesized and tested for potential anti-tumour activity against the human breast cancer cell line MDA-MB-435S using a so-called MTT assay in phosphate-buffered saline; ma = 3-hydroxy-2-methylpyran-4-onato, etma = 2-ethyl-3-hydroxypyran-4-onato, metro = 2-methyl-5-nitro-1H-imidazole-1-ethanol (metronidazole); MTT = 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide. The complexes exhibit lower IC50 values than our previously reported Ru(III) tris-maltolato and -ethylmaltolato complexes [D.C. Kennedy, A. Wu, B.O. Patrick, B.R. James, Inorg. Chem. 44 (2005) 6529–6535]. An improved synthetic route to the 2-nitroimidazole EF5 (2-(2-nitro-1-H-imidazol-1-yl)-N-(2,2,3,3,3-pentafluoropropyl)acetamide) is reported, as well as a related synthesis of a 3-nitro-1,2,4-triazole derivative of EF5, triF5 (2-(3-nitro-1-H-triazol-1-yl)-N-(2,2,3,3,3- pentafluoropropyl)acetamide). The complexes [RuL2(EF5)2]CF3SO3 (4a and 4b) and [Ru(ma)2(triF5)2]CF3SO3 (5) were prepared from the [RuL2(EtOH)2]CF3SO3 complexes (3a and 3b); IC50 values for 3–5 are high. Data on the uptake of Ru by the cells are also reported. The complexes were characterized generally by all or some of the following methods: elemental analyses, NMR, IR and mass spectroscopies, conductivity, and cyclic voltammetry; complexes 1a and 1b were also analyzed by X-ray crystallography.  相似文献   

19.
Kefzol (kzl), a β-lactam antibiotic, possesses various donor sites for interaction with transition metal(II) ions [Co(II), Cu(II), Ni(II) and Zn(II)] to form complexes of the type [M(kzl)2]Cl2 and [M(kzl)Cl], with molar ratio of metal: ligand (M:L) of 1:2 and 1:1 respectively. These complexes were prepared and characterized by physicochemical and spectroscopic methods. Their IR and NMR spectra suggest that kefzol potentially acts as a bidentate, tridentate as well as monoanionic tetradentate ligand. The complexes have been screened for antibacterial activity and results were compared with the activity of the uncomplexed antibiotic against Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Escherichia coli and Proteus mirabilis. The metal complexes were found to be more potent against one or more bacterial species than the uncomplexed kefzol.  相似文献   

20.
A new series of compounds derived from thiophene-2-carboxamide were synthesized and characterized by IR, 1H-NMR and 13C-NMR, mass spectrometry and elemental analysis. These compounds were further used to prepare their Co(II), Ni(II), Cu(II) and Zn(II) metal complexes. All metal(II) complexes were air and moisture stable. Physical, spectral and analytical data have shown the Ni(II) and Cu(II) complexes to exhibit distorted square-planar and Co(II) and Zn(II) complexes tetrahedral geometries. The ligand (L1) and its Cu(II) complex were characterized by the single-crystal X-ray diffraction method. All the ligands and their metal(II) complexes were screened for their in-vitro antimicrobial activity. The antibacterial and antifungal bioactivity data showed that the metal(II) complexes were found to be more potent than the parent ligands against one or more bacterial and fungal strains.  相似文献   

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