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1.
Palladium(II) complexes of type [Pd(L)Cl2] [where L=2-aminopyridine-N-thiohydrazide (L1), (2-aminopyridine-N-thio)-1,3-propanediamine (L2), benzaldehyde 2-aminopyridine-N-thiohydrazone (L3) and salicylaldehyde-2-aminopyridine-N-thiohydrazone (L4)] have been synthesized. The thiohydrazide, thiodiamine and thiohydrazones can exist as thione-thiol tautomer and coordinate as a bidentate N-S ligand. The ligands found to act in bidentate fashion. The complexes have been characterized by elemental analysis, IR, mass, electronic, 1H NMR spectroscopic studies, and TG/DTA study. Antifungal studies of some complexes were also carried out. Various kinetic and thermodynamic parameters like order of reaction (n), activation energy (E a), apparent activation entropy (S # ) and heat of reaction (ΔH) have also been carried out for one complex.  相似文献   

2.
The reactions of 3,10‐C‐meso‐3,5,7,7,10,12,14,14‐octamethyl‐1,4,8,11‐tetraazacyclotetradecadiene, L1, and two isomers (LB and LC, differing in the orientation of methyl groups on the chiral carbon atoms) of its reduced form with PdCl2 and K2[Pd(SCN)4], produce square‐planar tetrachloro‐ and tetrathiocyano‐palladium(II) complexes of general formulae [PdL′][PdCl4] and [PdL′][Pd(SCN)4] (L′ = L1, LB and LC), respectively. By contrast, the third ane isomer, LA, upon reaction with the same reagents, PdCl2 and K2[Pd(SCN)4], formed octahedral tetrachloro‐ and tetrathiocyanato‐palladium(IV) complexes [PdLACl2]Cl2 and [PdLA(SCN)2](SCN)2, respectively. The [PdL′][PdCl4] and [PdLACl2]Cl2 complexes undergo substitution reactions with KSCN to form square‐planar and octahedral tetrathiocyanato complexes [PdL′][Pd(SCN)4] and [PdLA(SCN)2](SCN)2, respectively. All complexes have been characterized on the basis of analytical, spectroscopic, conductometric and magnetochemical data. The anti‐fungal and anti‐bacterial activities of these complexes have been studied against some phytopathogenic fungi and bacteria. The crystal structure of [PdL1][Pd(SCN)4] has been confirmed by X‐ray crystallography and shows with square‐planar PdN4 and PdS4 geometries [monoclinic, space group C2/c, a = 17.884(3) Å, b = 14.734(2) Å, c = 11.4313(18) Å, β = 104.054(5)° ]. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

3.
在不同反应条件下反应得到了两种1,2,3-三唑衍生物的配合物[Co(H2O)6][Co(L13]2·4H2O(1)和Cu(L222)(HL1=5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid;HL2=1-(4-iodophenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid)。通过X射线单晶衍射和红外光谱确定了晶体结构,同时对配合物12进行了表面作用分析(Hirshfeld surface analysis),在二维指纹图谱中可以清楚的看到配合物中的主要分子间作用。  相似文献   

4.
Abstract

The reaction between 5,5-dimethyl-2-thioxoimidazolidin-4-one (H2L) and [PdCl4]2- has been studied in aqueous solution by potentiometric and spectrophotometric measurements. In the presence of the palladium salt, H2L is completely monodeprotonated (HL?); from spectrophotometric measurements, only two complexes having 1:1 and 1:2 Pd/ligand mol ratios have been identified. Potentiometric titrations, carried out on solutions with 1:1, 1:2, 1:3 and 1:4 metal/ligand mol ratios, show that these complexes must be formulated as Pd(HL)2 and [Pd2(HL)2(μ-H2O)(μ-OH)]+. Ionization constants of the pure ligand and formation constants of the complexes give pH distribution curves of the various species and the spectra of the two complexes. From MeOH, S-coordinated Pd(H2L)nCl2 (n = 2–4) complexes have been separated in the solid state; from water, two complexes of formula Pd(H2L)(HL)Cl and Pd(HL)Cl have been obtained with HL? N,S-coordinated to the metal.  相似文献   

5.
The dinuclear cyclopalladated complexes [Pd(L1 or L2)(µ-X)]2 (HL1=5-alkyl-2-(4′-alkoxyphenyl)pyrimidine, HL2=3-(4′-alkoxyphenyl)-6-alkoxypyridazine, X=Cl?, CH2ClCOO?, CH2BrCOO?, CH3CHBrCOO?, CH2BrCH2COO?, CH3COO?) have been synthesized and characterized; their mesogenic properities were determined by DSC and polarizing microscopy. The effect of the bulk and the polarity of the bridging ligands on their mesogenic properties is discussed. The effect of the length of the alkyl chains on the mesogenic properties of these organometallic complexes has also been investigated.  相似文献   

6.
Four new mononuclear complexes, [Ni(L1)(NCS)2] (1), [Ni(L2)(NCS)2] (2), [Co(L1)(N3)2]ClO4 (3), and [Co(L2)(N3)2]ClO4 (4), where L1 and L2 are N,N′-bis[(pyridin-2-yl)methylidene]butane-1,4-diamine and N,N′-bis[(pyridin-2-yl)benzylidene]butane-1,4-diamine, respectively, have been prepared. The syntheses have been achieved by reaction of the respective metal perchlorate with the tetradentate Schiff bases, L1 and L2, in presence of thiocyanate (for 1 and 2) or azide (for 3 and 4). The complexes have been characterized by microanalytical, spectroscopic, single crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 14 are distorted octahedral geometries. The antibacterial activity of all the complexes and their constituent Schiff bases have been tested against Gram-positive and Gram-negative bacteria.  相似文献   

7.
Summary New complexes of the general formulae [MLA(H2O)2]-Cl2 (M=Ni or Cu), [MLAX2] (M=Co or Cu; X=Cl or Br), [NiLABr2]·H2O, [MLA] [MCl4] (M=Pd or Pt), [NiLB(H2O)2]Cl2·2H2O, [MLBCl2] (M=Co, Ni, Cu, Pd or Pt; X=Cl or Br) and [MLB] [MCl4] (M=Pd or Pt), where LA=N,N-ethylenebis(2-acetylpyridine imine) and LB=N, N-ethylenebis(2-benzoylpyridine imine), have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, t.g./d.t.g. methods, magnetic susceptibilities and spectroscopic (i.r., far-i.r., ligand field,1Hn.m.r.) studies. Monomeric pseudo-octahedral stereochemistries for the CoII, NiII and CuII complexes andcis square planar structures for the compounds [MLBX2] (M=Pd or Pt; X=Cl or Br) are assigned in the solid state. The molecules LA and LB behave as tetradentate chelate ligands in the CoII, NiII, CuII and Magnus-type PdII and PtII complexes, bonding through both the pyridine and methine nitrogen atoms. A bidentateN-methine coordination of the Schiff base LB is assigned in the [MLBX2] complexes (M=Pd or Pt; X=Cl or Br). The anomalous magnetic moment values of the CoII complexes are discussed.  相似文献   

8.
Four new heterobimetallic complexes [CuL1][MnCl4] (1), [CuL2][MnCl4] (2), [NiL1][MnCl4] (3), [NiL2][MnCl4] (4) (L1?=?4,6,6-trimethyl-1,9-diamino-3,7-di-aza-nona-3-ene; L2?=?1,15-dihydroxy-7,9,9-trimethyl-3,6,10,13-tetra-aza-pentadeca-6-ene) have been prepared from elemental metals, ethylenediamine dihydrochloride or its N-(2-hydroxyethyl) derivative and acetone by the template condensation reaction. All complexes have been characterized by elemental analysis, IR and UV-Visible spectroscopy. The structures of 2 and 3 have been determined by X-ray crystallography (2: Orthorhombic, Pna2 1, a?=?20.136(4), b?=?11.185(2), c?=?10.251(2)Å, Z?=?4; 3: Orthorhombic, Pca2 1, a?=?14.335(2), b?=?11.405(2), c?=?11.154(2)Å, Z?=?4 ). Both crystals consist of alternating complex cations [ML]2+ and anions [MnCl4]2? linked together by N–H···Cl–Mn and O–H···Cl–Mn hydrogen bonds forming 2D corrugated sheets in (2) and 1D helical chains in (3). Complex 2 represents the first single crystal structure elucidation of the complex containing L2.  相似文献   

9.
Abstract

Four new mononuclear Schiff base manganese(III) and cobalt(III) complexes viz. [Mn(L1)(NCS)] (1), [Mn(L2)(NCS)] (2), [Co(L3)(NCS)] (3), and [Co(L4)(NCS)]·0.5CH3OH·0.5H2O (4), containing thiocyanate as a common pseudohalide ion are reported. The pentadentate Schiff base ligands H2L1, H2L2, H2L3, and H2L4 were obtained by the condensation of substituted salicylaldehydes with N-(3-aminopropyl)-N-methylpropane-1,3-diamine. The syntheses of the complexes have been achieved by the reaction of manganese(II) perchlorate or cobalt(II) perchlorate with the respective Schiff bases in the presence of thiocyanate in methanol medium. Complexes 14 have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 14 adopt nearly similar structures containing the MN4O2 (M?=?Mn, Co) chromophore in which each central M(III) ion adopts a distorted octahedral geometry. Weak intermolecular H-bonding interactions are operative in these complexes to bind the molecular units. The antibacterial activity of 14 and their constituent Schiff bases has been tested against some common bacteria.  相似文献   

10.
[Pd(cod)(cotl)]ClO4 (cod = 1,5-cyclooctadiene, cotl = cyclooctenyl, C8H13 ) undergoes substitutions with multidentate N-heterocycles: 1,3-bis(benzimidazolyl)benzene (L1), 1,3-bis(1-methylbenzimidazol-2-yl)benzene (L2), 2,6-bis(benzimidazolyl)pyridine (L3) and 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (L4) to yield mono/binuclear complexes: [Pd(cotl)(L1)(OClO3)], [Pd(cotl)(L)]ClO4 (L = L2 or L3) and [Pd(cotl)2(L4)](ClO4)2. Dihalobridged binuclear complexes [PdX(cotl)]2 (X = Cl or Br) undergo halogen bridge cleavages with the multidentate N-heterocycles to form binuclear complexes of the type [PdX(cotl)2L] (X = Cl or Br; L = L1, L2, L3 or L4). The complexes were characterized by elemental analyses, 1H-, 13C-n.m.r., i.r., far-i.r. and FAB-mass spectral studies.  相似文献   

11.
Five new palladium(II) complexes with 4-toluenesulfonyl-L-amino acid dianion and en, [Pd(en)(TsserNO)] (1), [Pd(en)(TsglyNO)] (2), [Pd(en)(TsalaNO)]?·?1.5H2O (3), [Pd(en)(TsleuNO)]?·?H2O (4), and [Pd(en)(TspheNO)]?·?2H2O (5), have been synthesized and characterized by elemental analysis, IR, UV, 1H NMR, and mass spectrometry. Crystal structure of 1 has been determined by X-ray diffraction analysis. The cytotoxicity was tested by MTT and SRB assays. The results indicate 15 exert cytotoxic effects against HL-60, Bel-7402, BGC-823, and KB cell lines and 5 displays the best cytotoxicity. The structure–activity relationships suggest that both amino acid and N-containing ligands have important effects on cytotoxicity.  相似文献   

12.
Three diacylthioureas 1,4‐C6H4[C(O)NHC(S)NHAr]2 (Ar = 2,6‐iPr2C6H3) ( L1 , 1 ), 1,3‐C6H4[C(O)NHC(S)NHAr]2 ( L2 , 2 ), and 1,3‐C6H4[C(O)NHC(S)NHAr′]2 (Ar′ = 2,6‐Me2C6H3) ( L3 , 3 ) were synthesized and characterized. The CuI complexes from the reactions of bipodal ligands Ln with CuX (X = Cl, Br, I) were structurally investigated by single‐crystal X‐ray diffraction methods. Treatment of L1 with CuX gave the metallamacrocyclic complexes ( L1 CuX)2 [X = Cl ( 4 ), Br ( 5 ), I ( 6 )] with the ligand to metal in a ratio of 2:2, where both sulfur and halide anions function as terminal substituents. In contrast, when L2 or L3 was reacted with CuBr, the two Ln ligands coordinate to four copper atoms each in a bridging and terminal fashion to yield [ Ln (CuBr)2]2 [n = 2 ( 7 ), 3 ( 8 )]. The obtained S4Cu4Br4 core contains all four bromide anions in bridging positions. The reaction of L3 with CuX (X = Cl, I) gave the 3:3 trinuclear complexes ( L3 CuX)3 [X = Cl ( 9 ) I ( 10 )], interconnected by halide bridges. The obtained diacylthioureas ( 1 – 3 ) and their CuI complexes ( 4 – 10 ) were also characterized by elemental analysis, FT‐IR, 1H and 13C NMR spectroscopy.  相似文献   

13.
The Schiff bases H2La, H2Lb, and H2Lc have been prepared from the reaction of 2-amino-4-chlorophenol with acetylacetone, benzoylacetone, and dibenzoylmethane, respectively. Organotin(IV) complexes [SnPh2(La)] (1), [SnPh2(Lb)] (2), [SnPh2(Lc)] (3), and [SnMe2(Lc)] (4) have been synthesized from the reaction of SnPh2Cl2 and SnMe2Cl2 with these Schiff bases. The synthesized complexes have been characterized by elemental analysis and FT-IR, 1H, 13C, and 119Sn NMR spectroscopy. Spectroscopic data suggest the Schiff bases are completely deprotonated and coordinated tridentate to tin via imine nitrogen and phenolic and enolic oxygen atoms; the coordination number of tin is five. Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activities of the Schiff bases and their complexes have been evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. H2La, H2Lc, and all complexes exhibited good activities and have potential as drugs.  相似文献   

14.
Copper(I) and palladium(II) complexes containing 5-acetyl-6-methyl-1,2,3,4-tetrahydropyrimidine-2-thione (L1), ethyl 4,6-dimethyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (L2), cis-5-acetyl-6-ethyl-5,6-dihydro-2-thiouracil (L3), and 5,6-dihydro-2-thiouracil (L4) have been synthesized. All complexes were characterized by elemental analysis, IR, 1H, and 13C NMR spectroscopy. To assign bands in the IR spectra of L1 and L2 and complexes with Cu(I) and Pd(II), deuterium substitution of movable protons at N-atoms was used. The crystal structures of two compounds, [Cu(L2)2Cl] and [Pd(L4)2Cl2], were determined by X-ray single-crystal and powder diffraction, respectively. In [Cu(L2)2Cl], copper has a rare coordination number of three and triangular surrounding of two neutral L2 molecules, coordinated through sulfurs, and chloride. In [Pd(L4)2Cl2], palladium has a standard square-planar geometry, formed by two uracil molecules and two chlorides. A new method for the synthesis of 5,6-dihydro-2-thiouracil, starting from β-aminopropionic acid, was suggested.  相似文献   

15.
Three new Cd(II) complexes consisting of phenanthroline derivative and organic acid ligands, formulated as [Cd3(3-PIP)2(L1)6] (I), [Cd(3-PIP)(L2)] · H2O (II), and [Cd(3-PIP)(L3)] (III) (3-PIP = 2-(3-pyridyl)imidazo[4,5-f]-1,10-phenanthroline, HL1 = 3,5-dinitrobenzoic acid, H2L2 = oxalic acid, H2L3 = benzene-1,3-dicarboxylic acid), have been synthesized via the hydrothermal reaction and characterized by single-crystal X-ray diffraction, elemental analyses and FT-IR spectra. Complex I is a trinuclear structure. Complex II features a 1D zigzag chain. Complex III shows a twisted double chain of binuclear units sustained by double carboxylate bridges. Three complexes are further extended into 3D supramolecular frameworks by hydrogen bonding and π-π-stacking interactions. The structural differences among I–III show that the organic carboxylates have important effects on the structures. Furthermore, the supramolecular interactions are the critical factors in determining the final structures of the complexes. In addition, the thermal stabilities and luminescent properties of complexes I and II are also investigated.  相似文献   

16.
The [Pd(cod)(cotl)]ClO4 complex (cod = cycloocta-1,5-diene; cotl = cyclooctenyl, C18H13 ) undergoes substitutions with new Schiff base ligands containing benzimidazole L [L = 2-(2-N-n-propylidenephenyl)benzimidazole (L1); 2-(2-N-i-propylidenephenyl)benzimidazole (L2); 2-(2-N-n-butylidenephenyl)benzimidazole (L3); 2-(2-N-i-butylidenephenyl)benzimidazole (L4)]. Facile displacement of cod by L occurs to produce complexes of the type [Pd(cotl)L]ClO4· nMe2CO (n= 0; L = L1, L2 or L3; n= 2, L = L4). Dihalobridge complexes of the type [Pd(cotl)X]2(X = Cl or Br) undergo halogen-bridge cleavage with L1–L4 to give mononuclear complexes of the type Pd(cotl)LX · nH2O (n= 2, X = Cl, L = L1; n= 0, X = Br, L = L1; n= 0, X = Cl, L = L2; n= 0, X = Cl or Br, L = L3; n= 0, X = Cl, L = L4; n= 2, X = Br, L = L4) and a binuclear complex [Pd(cotl)Br]2L2. The complexes were characterised by physical properties, i.r., 1H- and 13C-n.m.r. spectral techniques and by mass spectra. Probable structures have been proposed.  相似文献   

17.
Two new oxovanadium(V) complexes, [VOL1(OEt)(EtOH)] (1) and [VOL2(OMe)(MeOH)] (2), were prepared by reaction of [VO(acac)2] (where acac?=?acetylacetonate) with N′-(3-bromo-2-hydroxybenzylidene)-4-methylbenzohydrazide (H2L1) in ethanol and N′-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide (H2L2) in methanol, respectively. Crystal and molecular structures of the complexes were determined by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. The V ions have octahedral coordination. Thermal stability and the inhibition of urease of the complexes were studied.  相似文献   

18.
Twelve coordinate lanthanide (III) complexes with the general composition [Ln L3Xn(H2O)n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl?1, NO3 ?2, n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1- thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data.

Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands and their lanthanide complexes have been screened for their antifungal and antibacterial studies. Some of the synthesized lanthanide complexes have shown enhanced activity compared with that of the free ligand.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.  相似文献   

19.
Palladium(II) complexes of type [Pd(L)Cl2] [where, L?=?benzaldehyde-1,1-diphenyl-2-thiohydrazone (L1), salicylaldehyde-1,1-diphenyl-2-thiohydrazone (L2), acetaphenone-1,1-diphenyl-2-thiohydrazone (L3) and cyclohexanone-1,1-diphenyl-2-thiohydrazone (L4)] have been synthesized. The thiohydrazones can exist as thione-thiol tautomers and coordinate as a bidentate N–S ligand. The ligands are found to be monobasic bidentate. The complexes have been characterized by elemental analysis, IR, mass, electronic, 1H NMR spectroscopic studies. In vitro antifungal studies against fungi Aspergillus fumigatus, Aspergillus flavus and Aspergillus niger for some complexes have also been carried out.  相似文献   

20.
A new series of Ni(II) complexes, [Ni(L1)2] (1), [Ni(L2)2] (2), [Ni(L3)2] (3), and [Ni(L4)2] (4), were synthesized at ambient temperature. The bidentate Schiff base ligands HL1?4 have been obtained by the condensation reaction of 2-hydroxybenzaldehyde, 5-bromo-2-hydroxybenzaldehyde, 3-methoxy-2-hydroxy-benzaldehyde, and 4-methoxy-2-hydroxy-benzaldehyde, respectively, with 2-methoxyethylamine. The newly synthesized complexes were characterized by elemental analyses, FT-IR and UV–vis spectroscopy. The crystal structures of mononuclear Ni(II) complexes 2 and 3 were determined by the single-crystal X-ray diffraction technique. Electrochemical properties of the complexes were investigated in acetonitrile. The antioxidant properties of the Schiff base ligands and complexes were evaluated by two in vitro tests, DPPH radical scavenging and reducing power. The compounds were screened for their in vitro anticancer potential using gastric cancer cell lines by MTT assay. All ligands and complexes showed considerable cytotoxic activity against cancer cell lines (IC50 = 0.2516–5.468 μg·mL?1). The most promising result was achieved for complex 1 with the best IC50 value of 0.2516 μg·mL?1. It was found that the proliferation rate of MKN-45 cells decreased after treatment with the complexes in a dose-dependent way.  相似文献   

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