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1.
Summary Metal ion complexes of the thiosemicarbazone, 3-hexamethyleneimine-3-thiocarboxylic acid-2-[1-(2-pyridyl)-ethylidene]hydrazide (HLhexim) have been prepared and spectrally characterized. HLhexim coordinates primarily as the deprotonated tridentate ligand (i.e., pyridylN, azomethineN, and thione sulphur). The air oxidised cobalt(III) complex, [Co(LHexim)2] (BF4), was isolated from the preparation with cobalt(II) tetrafluoroborate, but other cobalt(II) salts yielded tetrahedral cobalt(II) compounds. Planar nickel(II) and copper(II) complexes were isolated from preparations with halide salts. Significant differences in the spectral properties of the various complexes are observed when compared to other thiosemicarbazones prepared from 2-acetylpyridine.  相似文献   

2.
Summary Metal ion complexes of the thiosemicarbazone,N-dimethyl-2-[1-(2-pyridinyl)ethylidene]hydrazinecarbothioamide (HL4DM) have been prepared and characterized spectrally. HL4DM coordinates primarily as the deprotonated tridentate ligand (i.e., pyrïdylN, azomethineN, and thione sulphur). In contrast to related thiosemicarbazones, oxidation to cobalt(III) does not occur during complex formation with cobalt(II) halides. Oxidation does occur on reflux with ethanolic Co(BF4)2, but we isolated a planar cobalt(II) complex as well. Only with the tetrafluoroborate salts of cobalt(II) and nickel(II) are complexes isolated containing the neutral thiosemicarbazone. Square planar [Ni(L4DM)X]complexes where X=Cl, Br, and OH have been isolated and e.s.r. spectra of a 1% Cu/Ni complex are compared to the results of other workers.  相似文献   

3.
Summary A series of metal ion complexes of the thiosemicarbazone,N-methyl-2[1-(2-pyridinyl)ethylidene]-hydrazinecarbothioamide (HL4M) has been prepared and spectrally characterized. HL4M coordinates either as a neutral bidentate ligand (i.e., pyridyl N and imine N) or as deprotonated tridentate ligand (i.e., pyridyl N, imine N and thiol sulphur). The cobalt(II) salts yield hexacoordinated cobalt(III) cations, and an isoelectronic species, [Ni(L4M)2], has been formed from Ni(C2H3O2)2. The remaining nickel(II) complexes involve the neutral ligand, as do two of the three copper(II) complexes. HL4M possesses a weaker ligand field and has less covalency in its bonding than related thiosemicarbazones that possess anN-dialkyl-function.  相似文献   

4.
An interesting series of cobalt(II) complexes of the new ligands: 4[N-(benzalidene)amino]antipyrinethiosemicarbazone (BAAPTS), 4[N-(2′-hydroxy-benzalidene)amino]antipyrinethiosemicarbazone (HBAAPTS) and 4[N-(2′-hydroxy-1′-naphthalidene)amino]antipyrinethiosemicarbazone (HNAAPTS) were synthesized by reaction with Co(II) salts in ethanol. The general stoichiometry of the complexes was found to be [CoX2(H2O)(L)] and [Co(L)2](ClO4)2, where X = Cl, NO3, NCS or CH3COO and L = BAAPTS, HBAAPTS or HNAAPTS. The complexes were characterized by elemental analysis, molar conductivity measurement, molecular weight determination, magnetic moments at room temperature, infrared and electronic spectra. All the thiosemicarbazones behave as neutral tridentate (N, N, S) donor ligands. The conductivity measurements in PhNO2 solution indicated that the chloro, nitrato, thiocyanato and acetate complexes are essentially non-electrolytes, while the perchlorate complexes are 1:2 electrolytes. Thermogravimetric studies were performed for some representative complexes and the decomposition mechanism proposed. Antibacterial and antifungal properties of the ligands and their cobalt(II) complexes have also been examined and it has been observed that the complexes are more potent bactericides than the ligand.  相似文献   

5.
Summary The ligand 3-azabicyclo[3.2.2]nonane-3-thiocarboxylic acid 2-[1-(2-pyridinyl)ethylidene]hydrazide (HL), which is observed in an unusual tautomeric form in the solid state, and its selenium analogue (HLSe) have been used to prepare a series of nickel(II) complexes. Compounds of the general formula [NiLX] (X=Cl, Br, NCS, N3, NO2 or NCSe) as well as [Ni(LSe)Cl] have been found to be diamagnetic, planar complexes. A single crystal study of [NiL(NCS)] shows the deprotonated ligand bound in a tridentate mannervia its pyridyl nitrogen, imine nitrogen and the thione sulphur atom with the nitrogen atom of the thiocyanato-ligand occupying the fourth coordination position. The solids prepared from the nickel(II) salts having tetrafluoroborate, nitrate and iodide ions approximate to octahedral symmetry and have neutral HL ligands coordinated in a bidentate fashionvia the pyridine and imine nitrogens with the remaining coordination sites being occupied by the anions or water molecules. The [NiL2] solid is also octahedral with the two deprotonated ligands bonding as tridentate groupsvia the same atoms as in the [NiLX] complexes.  相似文献   

6.
Summary The chlorides and bromides of cobalt(II), nickel(II) and copper(II) along with the acetates of the latter two metal ions and copper(II) tetrafluoroborate were used to prepare complexes ofN-2-(5-picolyl)-N-phenylthiourea (5MTUH). 5MTUH coordinates as a bidentate ligand via the pyridyl nitrogen and the sulphur atoms in the cobalt(II) complexes and the compounds isolated with Cu(BF4)2 and CuCl2. Complexes of stoichiometry [Cu(5MTU)X] (X=Br or C2H3O2) appear to have the deprotonated ligand coordinated via the pyridyl andN thioamide nitrogens and the sulphur atom. The nickel(II) complexes involve monodentate 5MTUH with sulphur being the donor atom. A violet, octahedral [Co(5MTUH)2Cl2] complex and a blue, tetrahedral [Co(5MTUH)Cl2] complex have been isolated, but with CoBr2 only an octahedral complex could be prepared.  相似文献   

7.
Summary The pseudo-macrocyclic dioxime ligand [(1) = LH] has been synthesized. A variety of cobalt(III) complexes, trans-[CoLX2], have been prepared and characterized (X = Cl, Br, NO2, NCS or N3) and [CoLCl(NO2)]. Vis. and i.r. spectra of the complexes are reported and aspects of the solution chemistry of the complexes studied.  相似文献   

8.
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   

9.
Summary Complexes of chromium(III), iron(III), cobalt(III), nickel(II) and copper(II) with salicylaldehyde N(1-piperidyl) thiocarbonyl hydrazone (spthH2), salicylaldehyde N-(1-morpholyl) thiocarbonyl hydrazone (smthH2), 2-hydroxy 4-methyl acetophenone N-(1-piperidyl) thiocarbonyl hydrazone (apthH2) and 2-hydroxy 4-methyl acetophenone N-(1-morpholyl) thiocarbonyl hydrazone (amthH2) have been prepared and characterized by analytical, spectral and magnetic measurements. Mixed ligand complexes of CuII-thiocarbonyl hydrazones and heterocyclic bases have been isolated. Depending on the nature of the metal salts used and the reaction conditions the thiocarbonyl hydrazones act as neutral or dibasic tridentate ligands.  相似文献   

10.
Summary The chelating behaviour of neutral and deprotonated 2,6-diacetyl-pyridine bis(2-furoylhydrazone), H2dapf, has been investigated in some new complexes of oxovanadium(IV), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II). The hydrazone reacts with the metal salts to yield complexes of two types; the addition compounds [VO(H2dapf)]SO4, [M(H2dapf)Cl]Cl and the deprotonated complexes [M(dapf)H2O] [M=manganese(II), cobalt(II), nickel(II), copper(II) or zinc(II)] in neutral and alkaline media, respectively. The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility, electronic, i.r. and e.s.r. studies and their stereochemistries are discussed.  相似文献   

11.
2-Formyl-, 2-acetyl- and 2-benzoylpyridine N(4)-cyclohexylsemicarbazone and N(4)-cyclohexylthiosemicarbazone complexes of cobalt(II, III), nickel(II) and copper(II) have been prepared and characterized by molar conductivities, magnetic susceptibilities and spectroscopic techniques. For many of the complexes, coordination is by the neutral ligand, the main exceptions being the cobalt(III) complexes of the three thiosemicarbazones and three of the benzoylpyridine derivatives. Thus, bonding is via the pyridyl nitrogen, azomethine nitrogen and thione/thiolato sulfur. The five-coordinate copper(II) complex of 2-acetylpyridine N(4)-cyclohexylthiosemicarbazone, [Cu(HAc4CHex)Cl2], approaches square pyramidal stereochemistry with the basal Cu—Cl bond significantly shorter than the apical Cu—Cl bond. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

12.
A new vicinal dioxime ligand containing azo and thione chromophores, namely 1,3-bis[4-(phenyldiazenyl)phenyl]-2-thiooxaimidazoline-4,5-dione dioxime (bppH2), was synthesized by the reaction of cyanogen di-N-oxide with N,N′-bis(4-phenylazophenyl) thiourea in dichloromethane solution at −10 °C. Mononuclear complexes of bppH2 with nickel(II), cobalt(II), and copper(II) were synthesized. The complexes, [Ni(bppH)2], [Cu(bppH)2], and [Co(bppH)2] were characterized by several techniques using elemental analyses, conductivity measurements, FT-IR, and electronic spectral studies. The data suggest that the ligand coordinates through the N,N atoms, as do most vic-dioximes. The molar conductivities in DMF solution indicate nonelectrolytic nature for the complexes. Antimicrobial activities of the ligand and its metal complexes were estimated for five bacteria, namely Klebsiella pneumoniae, Micrococcus luteus, Mycobacterium smegmatis, Enterobacter cloaca and Bacillus megaterium and three fungi, namely Candida albicans, Kluyveromyces marxianus, and Rhodotorula rubra.  相似文献   

13.
The synthesis and characterisation by elemental analysis, conductivity, FTIR, UV–Visible, ESR and magnetic measurements are described for a series of complexes of nickel(II) and cobalt(II) with three ligands (H2L1–3) derived from reduced N, N′-o-Phenylenebis(salicylideneimine). The complexes formed are identified as neutral species, where the ligands are coordinated through N and O donor atoms. The formulae obtained for the complexes are: [CoL(H2O)2] with octahedral geometry and [NiL] with tetrahedral geometry. Their antifungal activity is evaluated towards human pathogenic fungi including yeasts of the Candida genus, some opportunistic moulds belonging to the Aspergillus, Scedosporium genus and some dermatophytes. The cobalt complexes show a significant growth inhibition of yeasts tested and also to fungi of the genus Scedosporium which is of interest because these fungi are usually poorly susceptible to current antifungal including Amphotericin B and Itraconazole, chosen as reference in this study. The activity data show that the metal complexes are more potent than the parent ligand.  相似文献   

14.
Ionic [Pd(LH)2(ClO4)2], neutral (PdL2) complexes of Pd(II) with hetarylamines derived fromdipyridylamine and benz[c,d]indolylamine were synthesized. The 1H NMR, IR, and UV spectra of the products were studied. Irradiation of neutral Pd(II) complexes with N-derivatives of benz[c,d]indolylamine results in ligand elimination. Photolysis of a neutral Pd(II) complex with 3,5-dichloro-2,2'-dipyridylamine in solution results in ligand cyclization to give 8-chlorodipyrido[1,2-a:2',3'-d]imidazole.  相似文献   

15.
Summary TheN-methyl-2-[1-(2-pyridinyl-1-oxide)ethylidene]hydrazinecarbothioamide, HLO4M, has been used to prepare a series of CoIII, NiII and CuII complexes. Species with two deprotonated LO4M ligands, one LO4M and one HLO4M ligand, two HLO4M ligands and one HLO4M ligand with two small anionic ligands have been isolated. The deprotonated LO4M bonds as a tridentate ligandvia theN-oxide oxygen, the imine nitrogen (N1 and the sulphur while the HLO4M ligand coordinates primarily as a bidentate ligandvia only the first two atoms listed above. I.r., electronic, mass and e.s.r. spectra have been used to determine the nature of these complexes. One of the more striking differences between these compounds and those prepared with other thiosemicarbazones of 2-acetylpyridine and 2-acetylpyridineN-oxide is that tetrahedral yellow [Ni(HL)X2] rather than planar brown [NiLX] (X=Cl or Br) solids have been isolated with this ligand. Other differences in the nature of the coordination spheres of the various metal ions occur with this particular ligand when compared to previously studied thiosemicarbazone complexes.NATO Fellow, on leave from Medical Faculty, Istanbul University.  相似文献   

16.
Three new potentially hexadentate N4O2 Schiff-base ligands (H2L1, H2L2 and H2L3) were prepared from the reaction of the polyamines N,N′-bis(2-aminophenyl)-1,2-ethanediamine (L1), N,N′-bis(2-aminophenyl)-1,3-propanediamine (L2) and N,N′-bis(2-aminophenyl)-1,4-butanediamine (L3), respectively with salicylaldehyde. Reaction of the Schiff bases with Ni(II) salts in the presence of N(Et)3 gave the neutral complexes [NiL4], [NiL5] and [NiL6]. Ni(II) complexes of the polyamines were also prepared. One of complexes [Ni(L1)(MeCN)2](ClO4)2·MeCN has been characterized through X-ray diffraction methods.  相似文献   

17.
N′-(4′-Benzo[15-crown-5]naphthylaminoglyoxime (H2L) and its sodium chloride complex (H2L·NaCl) have been prepared from 2-naphthylchloroglyoxime, 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II) and copper(II) complexes of H2L and H2L·NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF2+-capped Ni(II), Co(III) and mononuclear complexes of thevic-dioxime were prepared. The macrocyclic ligands and their transition metal complexes have been characterized on the basis of IR, 1H NMR spectroscopy and elemental analyses data.  相似文献   

18.
The synthesis and molecular structure of trans‐{bis[(acetato‐κO)‐(2‐(1‐aziridinyl)ethanol‐κ2N,O)]}cobalt(II) ( 4 ) and cis‐{bis[chlorido‐(2‐(1‐aziridinyl)ethanol‐κ2N,O)]}cobalt(II) ( 5 ) is reported. Both neutral chelate complexes are prepared from the corresponding CoII salt [CoX2; X = OAc ( 1 ), Cl ( 2 )] and 2‐(1‐aziridinyl)ethanol (azolH, 3 ) in dry dichloromethane. A third, ionic complex, cis‐{bis[aqua‐(2‐(1‐aziridinyl)ethanol‐κ2N,O)]}cobalt(II) diacetate ( 6 ) is formed from 4 in the presence of water and could be crystallized from aqueous dichloromethane. In all cases, 2‐(1‐aziridinyl)ethanol is coordinating as bidentate chelate ligand by the nitrogen and oxygen atom of the aziridinyl and hydroxy moiety. After purification, the compounds have been fully characterized using IR spectroscopy and FAB+‐MS. The single‐crystal X‐ray structure analysis revealed a distorted octahedral geometry for all complexes with either trans ( 4 ) or cis ( 5 , 6 ) configuration.  相似文献   

19.
Complexes of CrIII, MnII, FeIII, CoII, NiII and CuII containing a macrocyclic pentadentate nitrogen–sulphur donor ligand have been prepared via reaction of a pentadentate ligand (N3S2) with transition metal ions. The N3S2 ligand was prepared by [1 + 1] condensation of 2,6-diacetylpyridine with 1,2-di(o-aminophenylthio(ethane. The structures of the complexes have been elucidated by elemental analyses, molar conductance, magnetic susceptibility measurements, i.r., electronic and e.p.r. spectral studies. The complexes are of the high spin type and are six-coordinate.  相似文献   

20.
Octahedral iron(II) and cobalt(II) based complexes, [N,N′-di(quinoline-2-methylene)-1,2-phenylenediimine]MCl2, and [N,N′-di(quinoline-2-methylene)diiminocyclohexane]MCl2 (M = Co and Fe), bearing tetradentate diimino nitrogen ligands were prepared and used in tert-butylacrylate (t-BA) polymerization after activation with methylaluminoxane (MAO). In general, polyacrylates with high molar mass and narrow molar mass distribution (MMD ≈ 2) were obtained. In order to understand the influence of the ligand on the polymerization process, polymerization behaviour of the hexacoordinated complexes was compared to pentacoordinated iron(II) and cobalt(II) complexes, 2,6-bis[1-(cyclohexylimido)ethyl]pyridine MCl2 (M = Co and Fe), bearing tridentate diimine nitrogen ligands as well as to free iron(II) chloride. The ability of the MAO activated hexacoordinated complexes to polymerize methylacrylate (MA) and methyl methacrylate (MMA) was also considered, but reduced activities as well as lower molar mass polymers were obtained than in the experiments with t-BA.  相似文献   

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