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1.
Summary New complexes of general formula [M(NNS)X] (NNS = anion of the Schiff base of 2-aminobenzaldehyde with S-methyldithiocarbazate; M = Ni, Cu, Pd or Pt; X = Cl, Br, I, NCS, NO3 or AcO), [Ni(NNS)(HNNS)]NO3 and [Co(NNS)2]Cl were prepared and characterised. The magnetic and spectral evidence suggests a square-planar structure for the mono-ligated complexes and an octahedral structure for the bis-chelated complexes. The copper(II) complexes have been shown to display high antifungal activities against the pathogenic fungi, Alternaria alternata and Curvularia geniculata.  相似文献   

2.
Summary New complexes of general formulae [Ni(HL)2], [ML]·H2O and [Cu(HL)X] (H2L = pyrrole-2-aldehyde Schiff bases ofS-methyl- andS-benzyldithiocarbazates; X = Cl or Br; M = NiII, CuII, ZnII or CdII) were prepared and characterized by a variety of physicochemical techniques. The Schiff bases coordinate as NS bidentate chelating agents in [Ni(HL)2] and [Cu(HL)X], and as tridentate NNS chelates in [ML] (M = NiII, CuII, ZnII or CdII). Both the [Ni(HL)2] and [NiL] complexes are diamagnetic and square-planar. Based on magnetic and spectroscopic evidence, thiolate sulphur-bridged dimeric square-planar structures are assigned to the [Cu(HL)X] and [ML] (M = NiII or CuII) complexes. The complexes ML (M = ZnII or CdII) are polymeric and octahedral.  相似文献   

3.
New cadmium(II) complexes of empirical formulae, [Cd(dpksme)X] (dpksme = anionic form of the Schiff base; X = NCS, Cl, I) and [Cd(dpksme)2] · 0.5MeOH, respectively have been prepared and characterized. The mono-ligated cadmium(II) complexes, [Cd(dpksme)X] are four-coordinate and tetrahedral but the bis-ligand complex, [Cd(dpksme)2] · 0.5MeOH is six-coordinate and octahedral. The crystal and molecular structure of [Cd(dpksme)2] · 0.5MeOH has been determined by X-ray diffraction. The complex has a distorted mer-octahedral structure in which the ligands are coordinated as uninegatively charged tridentate chelating agents via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. The distortion from regular octahedral geometry is ascribed to the restricted bite angles of the ligands. The Schiff base and its cadmium(II) complexes exhibit mild antibacterial activities against Shigella dysenteriae, Bacillus cereus, Staphylococcus aureus and Escherichia coli. They are also mildly fungitoxic against the phytopathogenic fungi, Alternaria alternata and Macrophomina phaseolina.  相似文献   

4.
Summary 2-Acetylpyridine N(4)-dihexyl- and N(4)-dicyclohexylthiosemicarbazone, HAc4DHex and HAc4DCHex, respectively, and FeIII, CoII, CoIII, NiII, CuII and ZnII complexes have been prepared and characterized by molar conductivities, magnetic susceptibilities and spectroscopic techniques. For many of the complexes, loss of the N(2)H hydrogen occurs, and the ligands coordinate to the metal centres as NNS monoanionic, tridentate ligands, e.g., [M(NNS)X] (M = CoII, NiII, CuII, NNS = Ac4DHex or Ac4DCHex and X = Cl or Br), [Fe(NNS)2]ClO4, [Co(NNS)2]BF4, [Cu(NNS)NO3] and [Zn(NNS)OAc]. ZnII ion is also chelated by neutral ligands in [Zn(HNNS)X2] (X = Cl, Br). In addition, [Ni(Ac4DHex)-(HAc4DHex)]X (X = BF4, ClO4) and [Ni(HAc4DCHex)2]-(BF4)2 are reported where the neutral thiosemicarbazone is coordinated via the pyridyl nitrogen, azomethine nitrogen and thione sulfur. Crystal structure determinations of HAc4DCHex and [Cu(Ac4DHex)Br] show the former to contain the bifurcated hydrogen bonded form and the latter to be planar with no significant interaction between neighbouring centres.  相似文献   

5.
Summary Metal ion complexes of 2-acetylpyridineS-methyldithiocarbazate, HNNS, have been prepared and spectrally characterised. Preparations in EtOH yield complexes in which the deprotonated ligand, NNS, is complexedvia its pyridyl nitrogen, azomethine nitrogen, and thione sulphur. The stoichiometries are: [M(NNS)2]X (M=Fe3+, Co3+ and X=ClO 4 , [FeCl4], BF 4 , 1/2 [CoCl4]2– and 1/2 [CoBr4]2–), [M(NNS)X] (M=Ni2+, Cu2+ and X=Cl, Br), [Cu(NNS)H2O]BF4 and Ni(HNNS)(NNS)F(EtOH)]BF4. The spectral (i.e., i.r., u.v.-vis.-n.i.r. and e.s.r.) and physical properties of these complexes are compared to those of theS-methyldithiocarbazates of 2-formylpyridine and 2-acetylpyridineN-oxide, as well as the related thiosemicarbazones prepared from 2-acetylpyridine. Thermal studies of the nickel(II) complexes indicate that the nature of thermal decomposition of coordinated NNS is different from that of HNNS.  相似文献   

6.
Summary New metal complexes [M(NNNS)X] (M = NiII, CuII, ZnII and CdII; NNNS = anion of the quadridentate ligands formed from S-methyl--N-(2-aminophenyl)-methylenedithiocarbazate and pyridine-2-aldehyde or 6-methylpyridine-2-aldehyde; X = Cl, NCS, NO3 or I) and [Co(NNNS)Cl2]·2H2O have been prepared and characterized by elemental analysis and conductance measurements. Magnetic and spectroscopic evidence support a five-coordinate structure for [M(NNNS)X] (M = NiII, CuII, ZnII and CdII; X = Cl, NCS) and a squareplanar structure for [Ni(NNNS)]X (X = NO3 or I). The [Co(NNNS)Cl3]·2H2O complex is low-spin and octahedral. The Schiff bases and some of their metal complexes were tested against three pathogenic fungi, Alternaria alternata, Curvularia geniculata and Fusarium palidoroseum. The metal complexes are less fungitoxic than the free ligands.  相似文献   

7.
Nickel(II) complexes of general empirical formula, NiLX·nH2O (L = deprotonated form of the Schiff base formed by condensation of N-methyl-S-methyldithiocarbazate with 2-hydroxybenzaldehyde or 5-bromo-2-hydroxybenzaldehyde; X = Cl, Br, NCS, AcO or CN; n = 0, 1) have been prepared and characterized by a variety of physico-chemical techniques. Magnetic and spectroscopic data support a square-planar structure for these complexes. The crystal structure of the [Ni(ONMeS)CN]·H2O complex (ONMeS = anionic form of the 2-hydroxybenzaldehyde Schiff base of N-methyl-S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the Schiff base is coordinated to the nickel(II) ion as a uninegatively charged anion coordinating via the phenolic oxygen atom, the azomethine nitrogen atom and the thione sulfur atom. The fourth coordination position is occupied by a cayano ligand. The antifungal properties of the Schiff bases and their nickel(II) complexes were studied against three plant pathogenic fungi. The ligands display moderate fungitoxicities against these organisms but their nickel(II) complexes are less active than the free ligands.  相似文献   

8.
《中国化学会会志》2017,64(9):1104-1110
A new unsymmetrical tridentate NNS Schiff base ligand, 2‐(2‐nitrophenylthio)‐N‐((pyridine‐2‐yl)methylene)benzenamine (L), and its Mn(II ), Ni(II ), Cu(II ), and Zn(II ) complexes were synthesized. These compounds were characterized by different physicochemical and spectroscopic techniques. The molecular structure of [NiL2 ](ClO4 )2 was determined by single‐crystal X‐ray diffraction. In this complex, two ligands coordinate through azomethine‐N, pyridine‐N, and thioether‐S, forming a mononuclear 6‐coordinate distorted octahedral geometry about a nickel.  相似文献   

9.
New complexes of general empirical formula, [M(NS)2] · nCHCl3 (M = NiII, CuII, PdII or PtII; NS = anionic form of the thiophene-2-aldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate; n = 0, 1) have been synthesized and characterized by physico-chemical techniques. Magnetic and spectroscopic evidence support a square-planar structure for these complexes. The crystal structures of the [Ni(tasbz)2] and [Cu(tasbz)2] · CHCl3 complexes (tasbz = anionic form of the thiophene-2-aldehyde Schiff base of S-benzyldithiocarbazate) have been determined by X-ray diffraction. Both complexes have a trans-planar structure in which the two Schiff base ligands are coordinated to the metal(II) ion as uninegatively charged bidentate ligands via the thiolate sulfur and the azomethine nitrogen atoms. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

10.
Copper(II) complexes of general formula, Cu(NNS)X 2 · nH2O (NNS = the 2-formylpyridine Schiff base of N-methyl-S-methyldithiocarbazate; X = Cl, Br, I, NCS; n = 0, 2) have been synthesized and characterized by elemental analysis and by magnetic and spectroscopic techniques. Based on magnetic and spectroscopic data, a monomeric five-coordinate square-pyramidal structure is assigned to these complexes. The crystal and molecular structure of [Cu(NNS)I2] has been determined by X-ray diffraction. The complex has a monomeric square-pyramidal structure with the ligand coordinated to the copper(II) ion via the pyridine nitrogen atom, the azomethine nitrogen atom and the thione sulfur atom. The fourth and fifth coordination sites are occupied by the iodide ligands. Antimicrobial tests indicate that Schiff base is inactive against the bacteria, Bacillus subtilis (mutant defective DNA repair), Pseudomonas aeruginosa, methicillin resistant Staphylococcus aureus and Bacillus subtilis (wild type) and weakly active against the fungi, Candida albicans, Candida lypolytica, Saccharomyces cereviseae and Aspergillus ochraceous but its copper(II) complexes, Cu(NNS)X 2 are strongly active against these organisms. A cytotoxicity study of the compounds against leukemic and cervical cancer cells showed that the Schiff base is inactive, but the complexes, [Cu(NNS)I2] and [Cu(NNS)(NCS)2] · 2H2O exhibit significant activity against cervical cancer cells with CD50 values of 4.8 and 4.2 g, respectively.  相似文献   

11.
New complexes of general formula, [M(NNS)Cl] (M = PdII, PtII; NNS = anionic forms of the 6-methyl-2-formylpyridine Schiff bases of S-methyl- and S-benzyldithiocarbazates) have been prepared and characterized by a variety of physico-chemical techniques. Based on conductance and spectral evidence, a square-planar structure is assigned to these complexes. The crystal and molecular structure of the [Pd(mpasme)Cl] complex (mpasme=anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted square-planar geometry with the ligand coordinated to the palladium(II) ion via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the fourth coordination position around the palladium(II) ion is occupied by the chloride ligand. The distortion from a regular square-planar geometry is ascribed to the restricted bite angle of the ligand. Both the Schiff bases exhibit strong cytotoxicity against the human ovarian cancer (Caov-3) cell lines, the S-methyl derivative being two times more active than the S-benzyl derivative. The [Pt(mpasme)Cl] complex is moderately active but the palladium(II) complex is weakly active against this cancer. None of the complexes of Hmpsbz are active against Caov-3. The Schiff base, Hmpasme exhibits moderate activity against the bacteria, MRSA, P. aeruginosa and S. typhimurium but is inactive against B. subtilis. Coordination of the ligand with palladium(II) substantially reduces its activity. The Schiff base, Hmpasbz and its palladium(II) and platinum(II) complexes are inactive against these bacteria. The Schiff bases and their palladium(II) and platinum (II) complexes are inactive against the pathogenic fungi, C. albican, Aspergillus ochraceous and Saccharomyces cerevisiae.  相似文献   

12.
Summary CuII, NiII, CoII, ZnII and PdII complexes of tridentate Schiff base ligands derived from the condensation of benzoic acid hydrazides with 2-aminonicotinaldehyde have been prepared and characterized. For M=Cu, Ni, Co and Zn the complexes were formulated as [M(ligand)(H2O)X] (X=Cl, Br), with a distorted octahedral geometry and tridentate Schiff base ligands. The Pd complexes were formulated as Pd(ligand)Cl2, with square planar geometries and bidentate Schiff base ligands. The e.s.r. spectra of the CuII complexes are discussed.  相似文献   

13.
Summary Metal(II) chelates of Schiff bases derived from the condensation of 1,2,3,5,6,7,8,8a-octahydro-3-oxo-N,1-diphenyl-5-(phenylmethylene)-2-naphthalenecarboxamide with o-aminophenol (KAAP), o-aminothiophenol (KAAT) or o-aminobenzoic acid (KAAB) have been prepared and characterized. The complexes are of the type [M(N2X)]2 for M = CuII and M(NX)2·nH2O for M = NiII, CoII and VOII (X = phenolic oxygen, thiophenolic sulphur or carboxylic oxygen; n = 0 or 2). Conductivity data indicate that the complexes are non-ionic. The Schiff bases behave as dibasic tridentate ligands in their copper(II) complexes and as monobasic bidentate ligands in their nickel(II), cobalt(II) and vanadyl(II) complexes. The subnormal magnetic moments of the copper(II) complexes are ascribed to an antiferromagnetic exchange interaction arising from dimerization. Nickel(II) and cobalt(II) complexes are trans octahedral whereas vanadyl(II) complexes are square pyramidal  相似文献   

14.
Two new pyrimidine based NNS tridentate Schiff base ligands S-methyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL1] and S-benzyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL2] have been synthesised by the 1:1 condensation of 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde and S-methyl/S-benzyl dithiocarbazate. A Ni(II) complex of HL1 and Co(III) and Fe(III) complexes of HL2 have been prepared and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and spectroscopic studies. All the bis-chelate complexes have a distorted octahedral arrangement with an N4S2 chromophore around the central metal ion. Each ligand molecule binds the metal ion using the pyrimidyl and azomethine nitrogen and thiolato sulfur atoms (except in the nickel complex, one ligand molecule uses the thione sulfur in lieu of thiolato sulfur atom). In the Ni(II) complex, one of the ligand molecules behaves as a neutral tridentate and the other molecule functions as a uninegative tridentate, whereas in the Co(III) and Fe(III) complexes, the ligand molecules behave as monoanionic tridentate. All the complexes were analyzed by single crystal X-ray diffraction and significant differences concerning the distortion from an octahedral geometry of the coordination environment were observed.  相似文献   

15.
New Schiff bases have been synthesized from benzofuran-2-carbohydrazide and benzaldehyde, [BPMC] or 3,4-dimethoxybenzaldehyde, [BDMeOPMC]; complexes of the type MLX2, where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II), L = BPMC or BDMeOPMC and X = Cl, have been prepared. Structures have been elucidated on the basis of elemental analysis, conductance measurements, magnetic properties, spectral studies i.e., 1H NMR, electronic, ESR and IR studies show that the Schiff bases are bidentate through the azomethine nitrogen and oxygen of the carbonyl. We propose tentative structures for all of these complexes. The antifungal and antibacterial activities of the ligands and their metal complexes have been screened against fungi Aspergillus niger and Aspergillus fumigatus and against bacteria Escherichia coli and S. aurious.  相似文献   

16.
Nickel(II) complexes of 12-membered macrocyclic ligands with different donating atoms (N2O2, N2S2 and N4) in the macrocyclic ring have been encapsulated in the nanocavity of zeolite-Y by the fexible-ligand method. Nickel(II) complexes with macrocyclic ligands were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of precursor ligand; 1,2-di(o-aminophenyl-, amino, oxo, thio)ethane, N2X2; in the supercages of the Ni(II)–NaY, and (ii) in situ condensation of the Ni(II) precursor complex; [Ni(N2X2)]2+; with glyoxal or biacetyl. The new host–guest nanocatalysts (HGNM), [Ni([R]2-N2X2)]2+–NaY (R = H, CH3; X = NH, O, S), have been characterized by FT-IR, DRS and UV–Vis spectroscopic techniques, XRD and elemental analysis, as well as nitrogen adsorption, and were used for oxidation of cyclohexene with molecular oxygen.  相似文献   

17.

Symmetrical bis (7-formyanil substituted-8-hydroxyquinoline-5-sulfonic acid), Schiff bases, react with Co(II), Ni(II) and Cu(II) ions to give MnL (n=1, 2) complexes as established by conductometric titration in 1 : 1 DMF: H2O. The complexes were identified by elemental analyses, molecular weight determination, thermal analysis, infrared, magnetic moments, electronic absorption, and electron spin resonance spectra. The suggested general geometry for these complexes may have a tetrahedral crystal structure and the general formula is [M2L(OH24], where M(II) = Co, Ni and Cu and L = 7―X―H2 L(―X―= dimethyl, p-phenyl, o-phenyl), while for the, trimethyl, ligand and the tetrahedral crystal structure has the general formula [M2L(OH2)2].Antimicrobial activity of these ligands and their transition metal complexes has been investigated on some common fungi and bacteria. A considerable increase in the biocide acticity of these ligands has been observed on coordination with transition metal ions, therefore, these complexes can be used in the chemotherapy of candidiaces and other fungal skin diseases.  相似文献   

18.
Mixed-ligand complexes of general formula, [Cu(NNS)(sac)] (NNS′ = S-benzyl-β-N-(2-acetylpyrid-2-yl)methylenedithiocarbazate, NNS″ = S-benzyl-β-N-(2-benzoylpyrid-2-yl)methylenedithiocarbazate and NNS? = S-benzyl-β-N-(6-methylpyrid-2-yl)methylenedithio-carbazate, sac = the saccharinate anion) have been synthesized by reacting [Cu(sac)2(H2O)4] · 2H2O with the appropriate ligands in ethanol and characterized by various physico-chemical techniques. Magnetic and spectral evidence indicate that the complexes are four-coordinate in which the Schiff bases coordinate as NNS ligands and the sac- anion coordinates as a unidentate N-donor ligand. An X-ray crystallographic structural analysis of [Cu(NNS′)(sac)] shows that the complex has a distorted square-planar geometry with the Schiff base coordinated to the copper (II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulphur atom while the fourth coordination position is occupied by the N-bonded saccharinate anion. The complexes have been evaluated for their biological activities against selected pathogens and cancer cell lines. They display weak activity against the pathogenic bacteria and fungi. The complexes were highly active against the leukemic cell line (HL-60) but only [Cu(NNS′)(sac)] was found to exhibit strong cytotoxicity against the ovarian cancer cell line (Caov-3). All complexes were inactive against the breast cancer cell line (MCF-7).  相似文献   

19.
Cleavage reactions of the dinuclear [{Ni(′S2C ′)}2] · DMF (′S2C ′ 2– = 1,3‐imidazolidinyl‐N,N′‐bis(2‐benzenethiolate)(2–)) with HNPiPr3 or HNSPh2 yielded the mononuclear complexes [Ni(NHPiPr3)(′S2C ′)] ( 1 ) and [Ni(NHSPh2)(′S2C ′)] ( 2 ) which have been completely characterized. The nickel‐carbene‐dithiolate [Ni(′S2C ′)] moiety is one of the very rare complex fragments that are able to coordinate both HNPR3 or HNSR2. IR spectra and X‐ray structure determinations show that 1 and 2 exhibit intramolecular N–H…S(thiolate) hydrogen bonds. Geometric parameters and NMR spectroscopic data of 1 and 2 are compatible with N–X single bonds and ylidic structures of the HNPiPr3 and HNSPh2 ligands. Comparison of Ni–N distances in diamagnetic and paramagnetic [Ni(NHSPh2)] complexes was rendered possible through the X‐ray structure determination of the homoleptic [Ni(NHSPh2)6]Cl2 ( 3 ) which formed as minor by‐product in the synthesis of 2 .  相似文献   

20.
Five new Ni(II) Schiff base complexes [NiLx(Solv)2] denoted by NiLx, x = 1–5, were synthesized and characterized. The Schiff base ligands were synthesized from the condensation of 5-bromo-2-hydroxy-3-nitrobenzaldehyde with different aliphatic and aromatic diamines. The X-ray crystal structure of NiL3 was determined. The ligands and complexes were tested as antibacterial agents against two gram(+) and two gram(?) human pathogenic bacteria. The complexes showed moderate antibacterial activity against both gram type bacteria. The new Ni(II) complexes showed enhanced antibacterial activity compared to the previously reported Cu(II) complexes of the same ligands.  相似文献   

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