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1.
Two ternary Cu(II) complexes of 1,10-phenanthroline (phen) and singly (Hsal(-)) or dideprotonated (sal(2-)) salicylate ligands were synthesized, their X-ray crystal structure and electron paramagnetic resonance spectral characteristics determined, and evaluated for anti-convulsant activities in the maximal electroshock (MES) and Metrazol models of seizure and Rotorod toxicity. The X-ray crystal structure of [bis(1,10-phenanthroline)-mu-bis(salicylato-O,O')dicopper(II)] dihydrate, 1, ([Cu(II)(2)(phen)(2)(sal)(2)].2[H(2)O]), shows it to be binuclear. This dimer consists of two centrosymmetrically related pseudo-five coordinate Cu(II) atoms 3.242(2) A apart and bridged by two dideprotonated salicylate ligands. The X-ray crystal structure of [bis(1,10-phenanthroline)(salicylato)copper(II)][salicylate] monohydrate, 2, ([Cu(II)(phen)(2)(Hsal)](+)[Hsal](-)[H(2)O]), shows it to be mononuclear. This complex cation exhibits a highly irregular distorted square pyramidal geometry about the Cu(II) atom, (4+1+1*). Each salicylate is singly deprotonated and one of them is ligand bonded in an asymmetric chelating mode. EPR results for 2 indicate that in concentrated DMF solution phen remains bonded to copper but salicylate is likely monodentate in contrast to the situation for 1. However, in dilute DMF solution, both 1 and 2 form the same species, which accounts for the similarity in anti-convulsant activity of the two compounds. Both 1 and 2 were found to be effective in preventing MES-induced seizures and ineffective in preventing Metrazol-induced seizures. Rotorod toxicity, consistent with central nervous system depression, paralleled the observed anti-convulsant activity. It is suggested that the observed anti-convulsant activity is consistent with central nervous system depression as a physiological mechanism in overcoming MES-induced seizures due to MES-induced brain inflammatory disease.  相似文献   

2.
The synthesis and characterization of ruthenium compounds of the type [RuCl2(NO)(dppp)(L)]PF6 [dppp = 1,3-bis(diphenylphosphino)propane; L = pyridine, 4-methylpyridine, 4-phenylpyridine and dimethyl sulfoxide] are described. The complexes were characterized by elemental analysis, UV/Vis and infrared spectroscopy, cyclic voltammetry, and X-ray crystallography for the complexes with the pyridine and 4-methylpyridine ligands. In vitro evaluation of these nitrosyl complexes revealed cytotoxic activity from 7.1 to 19.0 μM against the MDA-MB-231 breast tumor cells and showed that, in this case, they are more active than the reference metallodrug cisplatin. The 1,3-bis(diphenylphosphino)propane and the N-heterocyclic ligands alone failed to show cytotoxic activities at the concentrations tested (maximum concentration utilized = 200 μM).  相似文献   

3.
4.
The [Cu(sulfathiazolato)(2)(benzimidazole)(2)]2MeOH complex has been synthesised and characterised. It crystallises in the monoclinic system, space group C1c1, with unit cell dimensions a=18.829(7) A, b=12.206(3) A, c=17.233(5) A, alpha=90.06(2) degrees, beta=97.28(3) degrees, gamma=90.21(3) degrees and Z=4. The geometry around the copper(II) ion is intermediate between tetrahedral and square planar. The complex produces cleavage of plasmid pUC18 in presence of reducing agents. The efficiency of cleavage reaction of the title compound with pUC18 and with different reducing agents follows the order ascorbate-H(2)O(2)>ascorbate>MPA>dithiothreitol>H(2)O(2).  相似文献   

5.
Four ternary metal--ortho-iodohippurate (I-hip)--acyclovir (ACV) complexes, [M(I-hip)(2)(ACV)(H(2)O)(3)] where M is Co(II) (1), Ni(II) (2), Cu (3) and Zn(II) have been obtained by reaction between the corresponding binary complexes M(II)(I-hip)(2)xnH(2)O and ACV. Three ternary complexes (M=Co, Ni and Zn) and the corresponding Zn(II)--ortho-iodohippurate binary derivative have been structurally characterized by X-ray diffraction: The studies show these three ternary complexes are isostructural and present, in solid state, an interesting stacking between the nucleobase and the aryl ring of the hippurate moiety, which probably promotes the formation of ternary complexes. Moreover, the two different ligands interact between them by means of ancillary hydrogen bonds with water molecules coordinated to the metal ion. It must be mentioned that these two recognition factors, hydrogen bonds plus stacking, could explain the reason for the isostructurality of these ternary derivatives with so different three metal ions, with diverses trends in coordination numbers and geometries. In solid state, there are two enantiomeric molecules that are related by an inversion center as the crystal-building unit (as a translational motif) for the ternary complexes.  相似文献   

6.
The reactions of zinc and cadmium salts with 2,2′-biimidazole (H2biim) yielded a series of compounds in which the ligand is coordinated in the chelating bidentate mode. ZnCl2 and [Ag(H2biim)](NO3) in methanol in a 2:1 proportion produced Zn(H2biim)Cl2, in which the metal has a distorted tetrahedral coordination. A 1:2 ratio led to [Zn(H2biim)2(CH3OH)2](NO3)2, containing an octahedrally coordinated Zn(II) center with the O-bonded methanol ligands occupying trans positions. The corresponding [Cd(H2biim)2(CH3OH)2](NO3)2 compound was obtained from CdCl2. By starting with Cd(NO3)2 and Cd(ClO4)2 in aqueous media, the related octahedral bis-chelate compounds [Cd(H2biim)2(NO3)(H2O)](NO3) and Cd(H2biim)2(ClO4)2, respectively, were isolated, the apical positions being filled by perchlorate oxygens in the latter case. With Cd(BF4)2, the glass container participated in the reaction and a tris-chelate complex [Cd(H2biim)3]2(SiF6)(BF4)2 · 6EtOH was isolated. The [Cd(H2biim)3]2+ and ions define an extended hydrogen-bonded network, in which ions surrounded by disordered ethanol molecules occupy large cavities. The two free N-H groups provide H2biim with a unique ability to form hydrogen bonds and their interactions with counter anions or other acceptors play a determining role in controlling molecular packing. The IR spectra of all compounds are discussed.  相似文献   

7.
Two novel tridentate ligands, 2-(2-benzimidazole)-1,10-phenanthroline (PHBI) and 2-(2-naphthoimidazole)-1,10-phenanthroline (PHNI), and their heteroleptic complexes [Ru(tpy)(PHBI)](ClO(4))(2).2H(2)O (1) and [Ru(tpy)(PHNI)](ClO(4))(2).H(2)O (2) (tpy=2,2':6',2"-terpyridyl) have been synthesized and characterized by elemental analysis, mass spectra, 1H NMR, and electronic spectroscopy. The electrochemical behaviors of the two novel complexes were studied by cyclic voltammetry. The DNA-binding properties of the two complexes were investigated by spectroscopic methods and viscosity measurements. The results indicated that the two complexes interact with DNA in different binding modes. Complex 1 may bind to DNA via electrostatic interaction, while complex 2 binds to DNA by partial intercalation via the extended naphthyl ring into the base pairs of DNA.  相似文献   

8.
Two NNS tridentate Schiff base ligands of 2-benzoylpyridine S-methyldithiocarbazate (HL1) and 2-benzoylpyridine S-phenyldithiocarbazate (HL2) and their transition metal complexes [Cu2(L1)2(CH3COO)](ClO4) (1), [Zn2(L1)2(ClO4)2] (2), [Zn(L2)2](3) have been prepared and characterized by elemental analysis, IR, MS, NMR and single-crystal X-ray diffraction studies. In the solid state, each of two Schiff bases remains in its thione tautomeric form with the thione sulfur atom trans to the azomethine nitrogen atom. Under similar prepared conditions, three new complexes showed distinctly different coordination modes depending on their coordinating preferences. Each copper atom in S-bridged dinuclear complex [Cu2(L1)2(CH3COO)](ClO4) (1) is surrounded by five donor atoms in a square-pyramidal fashion (4 + 1). [Zn2(L1)2(ClO4)2] (2) is a dimer in which each zinc atom adopts a seven-coordinate distorted pentagonal bipyramidal geometry, while mononuclear [Zn(L2)2] (3) has octahedral coordination geometry. Biological studies, carried out in vitro against selected bacteria, fungi, and K562 leukaemia cell line, respectively, have shown that different substituted groups attached at the dithiocarbazate moieties and metals showed distinctive differences in the biological property. Zinc(II) complexes 2 and 3 could distinguish K562 leukaemia cell line from normal hepatocyte QSG7701 cell line. Effect of the title compounds on Mitochondria membrane potential (MMP) and PI-associated fluorescence intensity in K562 leukaemia cell line are also studied. The title compounds may exert their cytotoxicity activity via induced loss of MMP.  相似文献   

9.
The syntheses of five new complexes of the 2-formylpyridinethiosemicarbazone ligand (HFpyTSC) with Pd(II) and Rh(III) ions are described, viz., [Pd(FpyTSC)(PPh3)]PF6, [Pd(FpyTSC)(SCN)], [Pd(FpyTSC)Br], [Pd(HFpyTSC)2]Br2 and [Rh(FpyTSC)(PPh3)2Cl]ClO4. The formulation of the complexes is discussed in terms of their elemental analyses and IR, Raman, NMR (1H, 13C and 31P), mass and electronic spectra. The X-ray crystal structures of [Pd(FpyTSC)(PPh3)]PF6 and [Pd(FpyTSC)(SCN)] show that the HFpyTSC ligand coordinates to the central Pd(II) ion in a planar conformation through the pyridyl nitrogen, the azomethine nitrogen and the deprotonated thiol sulphur atom. Thus, HFpyTSC is a versatile ligand that usually acts as a mononegative tridentate ligand bonding through Npy, NCN and C-S while, in the case of [Pd(HFpyTSC)2]Br2, it behaves as a neutral bidentate ligand via NCN and CS.  相似文献   

10.
The new iridium(III) complex, imidazolium[trans(DMSO,imidazole)tetrachloroiridate(III)], (I) (DMSO=dimethyl sulfoxide), and the orange form of [(DMSO)(2)H][trans(DMSO)(2)tetrachloroiridate(III)], (II) have been prepared and characterized, both in the solid state and in solution, by X-ray diffraction and by various physicochemical techniques. Single crystal X-ray diffraction studies point out that complex (II) is isomorphous to the ruthenium(III) analogue, [(DMSO)(2)H][trans-RuCl(4)(DMSO)(2)], (III). Crystallographic data are the following: a=16.028(2) A, b=24.699(3) A, c=8.262(1) A, in space group Pbca (Z=8) for (imidazolium)[trans(DMSO,imidazole)tetrachloroiridate(III)], (I); and a=9.189(2) A, b=16.511(4) A, c=14.028(3) A, beta=100.82(2) degrees in space group P2/n (Z=4) for [(DMSO)(2)H][trans(DMSO)(2)tetrachloroiridate(III)], (II). Visible absorption spectra show that both complexes are stable for several days, at pH 7.4, at room temperature. No significant chloride hydrolysis is observed, even at high temperature (70 degrees C), over 24 h. The extreme stability of these iridium(III) complexes within a physiological buffer was further assessed by (1)H NMR; in addition, cyclic voltammetry measurements evidenced a high stability of the oxidation state +3. Preliminary biological studies show that both complexes do not bind appreciably bovine serum albumin nor inhibit significantly the proliferation of representative human tumor cell lines, suggesting that hydrolysis of coordinated chlorides is a crucial feature for the biological properties and the antitumor activity of the parent ruthenium(III) complexes.  相似文献   

11.
The [RhCl3(N-N)(DMSO)] complexes, the N-N being 2,2′-bipyridine (1), 1,10-phenanthroline (2), 4,7-diphenyl-1,10-phenanthroline (3), 4,4′-dimethyl-2,2′-bipyridine (4) and 1,10-phenanthroline-5,6-dione (5), have been synthesized and characterized with spectroscopic methods. The compounds 2-5 adopt mer- and complex 1fac-structure. The molecular and electronic structure studies of mer- and fac-complexes with bpy and phen ligands at the DFT B3LYP level with 3-21G∗∗ basis set showed that mer-isomers are more stable. The cytostatic activity of the [RhCl3(N-N)(DMSO)] complexes against Caco-2 and A549 tumor cells have been studied. Their antibacterial activity have also been investigated. It has been found that the very promising biological activity show complexes 2, 3 and 4.  相似文献   

12.
Three new Cu(II) complexes, [Cu2(C3H2O4)(phen)2(H2O)3](NO3)2(H2O)2 (1) (C3H2O4 = malonate, phen = 1,10-phenanthroline), [Cu2(C4H4O4)(phen)2(H2O)2](NO3)2 (2) (C4H4O4 = succinate), and {[Cu2(phen)2(H2O)(NO3)]2(C5H6O4)2}(NO3)2 (3) (C5H6O4 = glutarate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are of dinuclear copper(II) complexes bridged by malonate and succinate dianions, respectively, and 3 is a tetranuclear species formed by two {[Cu2(phen)2(H2O)(NO3)](C5H6O4)} fragments. The copper ions in 1 and 3 show square-pyramidal coordination geometry, while the copper ions in 2 exhibit a square planar geometry. In each complex, the dicarboxylate ligand is coordinated to copper ions as a chelate and monodentate (1), bis-monodentate (2), and bis-bridging ligand toward the copper ions with syn-syn coordination mode (3).  相似文献   

13.
Palladium(II) complexes with triphenylphosphine (PPh3) and thioamides of the general formulae, [Pd(L)2(PPh3)2]Cl2 and [Pd(L)2(PPh3)2] have been prepared and characterized by elemental analysis, IR and NMR (1H, 13C and 31P) methods, and two of them (trans-[Pd(PPh3)2(Dmtu)2]Cl2·(H2O)(CH3OH)0.5 (1) and trans-[Pd(PPh3)2(Mpy)2] (2)) by X-ray crystallography; where L = thiourea (Tu), methylthiourea (Metu), N,N′-dimethylthiourea (Dmtu), tetramethylthiourea (Tmtu), 2-mercaptopyridine (Mpy), 2-mercaptopyrimidine (Mpm) and thionicotinamide (Tna). The spectral data of the complexes are consistent with the sulfur coordination of thioamides to palladium(II). The crystal structures of the complexes show that (1) has ionic character consisting of [Pd(PPh3)2(Dmtu)2]+2 cations and uncoordinated Cl ions, while (2) is a neutral complex with Mpy behaving as anionic thiolate ligand. The coordination environment around palladium in (2) is nearly regular square-planar, while in (1) the trans angles show significant distortions from 180°. The complexes were screened for antibacterial effects, brine shrimps lethality bioassay and antitumor activity. These complexes showed significant activities in most of the cases against the tested bacteria as compared to that of a standard drug. Their antitumor activity against prostate cancer cells (PC3) is comparable with doxorubicin, together with no cytotoxic effects in brine shrimps lethality bioassay study.  相似文献   

14.
A series of octahedral and square-planar Ni(II) complexes have been synthesized from two different types of hydrazone ligands. The isolated complexes have been characterized by means of analytical and spectroscopic techniques. The structures of two of the complexes have been determined by single crystal X-ray diffraction study. The binding modes of the complexes with DNA and their ability to bind DNA have been investigated by UV-Vis absorption titration, ethidium bromide fluorescence displacement experiments, and viscometry measurements and cyclic voltammetry studies. The experimental results show that the mode of binding of the complexes to DNA is combination of different mode of interaction.  相似文献   

15.
The compounds [Cu(dien)(2-PhIm)(ClO4)](ClO4) (1); [Cu(dien)(2-MeBzIm)](ClO4)2 (2); where dien = diethylenetriamine, 2-PhIm = 2-phenylimidazole and 2-MeBzIm = 2-methylbenzimidazole, were synthesized and characterized. The complexes possessing [Cu(II)dien] moiety as common, the former containing 2-phenylimidazole, yielded square pyramidal geometry with apical perchlorate coordination [Cu1-O(5) = 2.449 Å], while the latter with 2-methylbenzimidazole formed square planar geometry with weak perchlorate contact [Cu1-O(8) = 2.596 Å] in its apical position. The effect of solvent and the variable temperature 1H NMR investigation combinedly explore the geometrical rearrangement towards five coordination around Cu(II) metal center by accommodating the solvent molecule in its fifth coordination. Possessing easily labile perchlorate anion, both these complexes were investigated for their oxidation capability using 3,5-di-tert-butyl catechol (DTBC). The rate constant determined for the oxidation of DTBC to corresponding quinone indicates that they are catalytically quite similar and the kcat of 1 ≈ 2. The crystal structure and the NMR investigations are discussed in detail.  相似文献   

16.
A family of complexes of Ni(II), 2-aminomethylpyridine (ampy) and tricyanomethanide (tcm) have been prepared and studied by IR, X-ray crystallography and variable temperature susceptibility. The complexes synthesized include [Ni(ampy)3](ClO4)2 (1), [Ni(ampy)3](tcm)(PF6) (2), [Ni(ampy)3](PF6)2 (3), [Ni(ampy)2(H2O)2]Cl2 (4), and [Ni(ampy)2(tcm)2] (5). No coordination polymers of tcm were obtained. The magnetic behavior of the complexes, and the known material [Ni(ampy)(NO3)2], is dominated by single-ion anisotropy effects with D-values in the range of −2 to −12 K, although some compounds show a weak antiferromagnetic interaction.  相似文献   

17.
The molecular tumor inhibiting titanium compound budotitane [Ti(IV)(bzac)(2)(OEt)(2)] (1) and its dichloro-derivative [Ti(IV)(bzac)(2)Cl(2)] (2) (bzac=1-phenylbutane-1,3-dionate) have been crystallized and characterized by X-ray crystallography and further physical methods. Budotitane (1) crystallizes in the tetragonal, non-centrosymmetric space group P4(1) with two molecules in the asymmetric unit. Both molecules adopt the cis-cis-trans configuration with the acetyl ends of the benzoylacetonate ligands in the trans position. The dichloro-derivative of budotitane, [Ti(IV)(bzac)(2)Cl(2)] (2) crystallizes in the monoclinic, centrosymmetric space group P2(1)/n with one molecule only in the asymmetric unit. In contrast to budotitane (1), (2) shows a cis-trans-cis arrangement with the benzoyl groups in the trans position. In both complexes there are equal numbers of Delta and Lambda enantiomers within the unit cell. The phenyl groups in (1) as well as in (2) are in approximately coplanar conjugation to the metal enolate rings. The thermal degradation of budotitane (1) was investigated in the temperature range from 25 degrees C up to 800 degrees C and reveals the formation of Ti(IV)O(bzac(2-)) as an intermediate and of the rutile phase of TiO(2) as a final product. It may be worthwhile to introduce budotitane in the form of isomerically pure crystals in the preparation of the drug used for future tests.  相似文献   

18.
This study evaluates the action of the new ruthenium complexes trans-RuCl(2)(nic)(4)] (I) and trans-[RuCl(2)(i-nic)(4)] (II) as free radical scavengers. In our experiments, both compounds acted as scavengers of superoxide anion (O(2)*(-)), hydroxyl radicals (HO*) and nitrogen monoxide (formally known as 'nitric oxide'; NO*). In addition, complexes I and II potentiated the release of NO* from S-nitroso-N-acetyl-DL-penicilamine (SNAP), a NO* donor. Complex II, but not I, also decreased the nitrite levels in culture media of activated macrophages. A hypsochromic shift of lambda(max) and a significant change in half-wave potential (E(1/2)) was observed when NO* was added to the Complex II. Thiobarbituric reactive substance (TBARS) levels were significantly reduced in rats treated for 1 week with Complex II plus tert-butylhydroperoxide, when compared to rats treated only with tert-butylhydroperoxide. None of the complexes showed cytotoxicity. These findings support the suggestion that the new ruthenium complexes, especially trans-[RuCl(2)(i-nic)(4)] or its derivatives, might provide potential therapeutic benefits in disorders where reactive nitrogen (RNS) or oxygen (ROS) species are involved.  相似文献   

19.
A series of Cu(II) coordination compounds with benzimidazole-derived bidentate chelating ligands have been prepared and characterized by X-ray crystallography. The 2-(4,5-dihydro-1H-imidazol-2-yl)-1H-benzimidazole CuCl2 complex 8 showed very potent superoxide dismutase (Cu,Zn-SOD) activity in vitro with IC50 of 0.09 microM, comparable to those described in the literature for best low molecular weight CuZnSOD mimics. Cytotoxicity studies with seven different human tumor cell lines in vitro showed that the most active 2-(4,5-dihydro-1H-imidazol-2-yl)-5-nitro-1H-benzimidazole CuCl2 complex 10 inhibited the growth of cancer cells with IC50 between 4.76 and 10.84 microM.  相似文献   

20.
Two isomeric gold(I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Au(L)(PPh3) (HL = pyrazole (1), imidazole (2)) were isolated as colorless cubic crystals for 1 and colorless plate crystals for 2, respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. These complexes were also fully characterized by complete elemental analyses, thermogravimetric/differential thermal analyses (TG/DTA) and FT-IR in the solid state and by solution NMR (31P, 1H and 13C) spectroscopy and molecular weight measurements in acetone solution. These complexes consisted of a monomeric 2-coordinate AuNP core both in the solid state and in solution. The molecular structures of 1 and 2 were compared with those of related gold(I) complexes, [Au(1,2,3-triz)(PPh3)] (3, Htriz = triazole), [Au(1,2,4-triz)(PPh3)]2 (4) as a dimer through a gold(I)-gold(I) bond in the solid state, and [Au(tetz)(PPh3)] (5, Htetz = tetrazole). Selective and effective antimicrobial activities against two gram-positive bacteria (B. subtilis, S. aureus) and modest activities against one yeast (C. albicans) found in these gold(I) complexes 1-4 are noteworthy, in contrast to poor activities observed in the corresponding silver(I) complexes.  相似文献   

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