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1.
Summary 2,3-Bis(hydroxyimino)-1,2,3,4-tetrahydro-pyrido[2,3-b]pyrazine (H2L), prepared from 2,3-diaminopyridine and cyanogen-di-N-oxide has been converted into nickel(II), palladium(II), copper(II), cobalt(II), and cobalt(III) complexes (H2L) with a 12 metal:ligand ratio. The ligands coordinate through the two N atoms, as do most vicinal dioximes. [(LH)Cl(H2O)Cd], contains a six-membered chelate ring. [Co(HL)2(L)Cl] has also been prepared using triphenylphosphine, triphenylarsine, thiophene and chloride as axial ligands. The structure of thevic-dioxime and its complexes are proposed on the basis of elemental analysis, i.r.,1H-n.m.r. and uv-visible measurements.  相似文献   

2.
Summary Nickel(II), palladium(II), cobalt(II) and copper(II) complexes of the ligandN,N-1,2-propane-bis(methyl 2-amino-cyclopent-1-ene-dithiocarboxylate) (H2L1),N,N-1,3-propane-bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate) (H2L2) andN,N-[bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate)] diethylenetriamine (H2L3) have been synthesised. Both H2L1 and H2L2 form complexes of the type ML, and all but the copper(II) complexes, are square planar. In the copper(II) complexes tetrahedral distortion is significantly more with CuL2. From H2L3 square planar complexes of the type [M(HL3)X] (M=Ni, X=Cl, Br, I or SCN; M=Pd, X=Cl or Br) have been obtained in which the donor unit involved is N2SX. The composition of the cobalt(II) and copper(II) complexes is [M(H2L3)X2] (X=Cl or Br) which contain the chromophore [MN3X2].  相似文献   

3.
Summary Copper(II), nickel(II) and cobalt(II) perchlorate complexes of 5,5-dimethylcyclohexane-1,2,3-trione-2-(p-nitrophenyl-hydrazone) (HL1), 5,5-dimethyl-cyclohexane-1,2,3-trione-2-(p-chlorophenylhydrazone) (HL2), 5,5-dimethylcyclohexane-1,2,3-trione-2-(o-chlorophenylhydrazone) (HL4), 5,5-dimethylcyclohexane-1,2,3-trione-2-(o-methylphenyl-hydrazone) (HL5) and 5,5-dimethylcyclohexane-1,2,3-trione-2-(m-methylphenylhydrazone) (HL6) have been prepared, and characterized using analytical, spectral and magnetic measurements. The data reveal that the reaction of Cu(ClO4)2 (1 mol) in EtOH, with all ligands, produces complexes of the type CuL(ClO4)(H2O).nH2O. Nickel(II) and cobalt(II) perchlorates react only with HL1 and HL2 to produce the complexes ML(ClO4)(H2O)3 (where M = NiII, L = L and L2, M = CoII, L = L1) and Co(HL2)2-(ClO4)2.2H2O. The spectral data show that the ligands behave as monobasic bidentate in their azo forms, except HL2 which reacts with cobalt(II) as a neutral bidentate ligand in its hydrazone form.  相似文献   

4.
The synthesis and characterization of new transition metal complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 3‐(2‐hydroxynaph‐1‐ylazo)‐1,2,4‐triazole ( HL1 ) and 3‐(2‐hydroxy‐3‐carboxynaph‐1‐ylazo)‐1,2,4‐triazole ( HL2 ) have been carried out. Their structures were confirmed by elemental analyses, thermal analyses, spectral and magnetic data. The IR and 1H NMR spectra indicated that HL1 and HL2 coordinated to the metal ions as bidentate monobasic ligands via the hydroxyl O and azo N atoms. The UV‐Vis, ESR spectra and magnetic moment data revealed the formation of octahedral complexes [Mn L1 (AcO)(H2O)3] ( 1 ), [Co L1 (AcO)(H2O)3]·H2O ( 2 ), [Mn L2 (AcO)(H2O)3] ( 6 ) and [Co L2 (AcO)(H2O)3] ( 7 ), [Ni L1 (AcO)(H2O)] ( 3 ), [Zn L1 (AcO)(H2O)]·H2O ( 5 ), [Ni L2 (AcO)(H2O)] ( 8 ), [Zn L2 (AcO)(H2O)]·10H2O ( 10 ) have tetrahedral geometry, whereas [Cu L1 (AcO)(H2O)2] ( 4 ) and [Cu L2 (AcO)(H2O)2]·5H2O ( 9 ) have square pyramidal geometry.. The mass spectra of the complexes under EI‐con‐ ditions showed the highest peaks corresponding to their molecular weights, based on the atomic weights of 55Mn, 59Co, 58Ni, 63Cu and 64Zn isotopes; besides, other peaks containing other isotopes distribution of the metal. Kinetic and thermodynamic parameters of the thermal decomposition stages were computed from the thermal data using Coats‐Redfern method. HL2 and complexes 6 – 10 were found to have moderate antimicrobial activities against Staphylococcus aureus (gram positive), Escherichia coli (gram negative) and Salmonella sp bacteria, and antifungal activity against Fusarium oxysporum, Aspergillus niger and Candida albicans. Also, in most cases, metallation increased the activity compared with the free ligand.  相似文献   

5.
Summary Metal complexes of the title ligands were characterized in order to determine the factors influencing the stability of chelate isomerism in the same molecule. The ligands were prepared by 1:1 condensation of isonitrosoacetylacetone (Hiso) with eithero-aminophenol (H2 isoaph),p-aminophenol (H2 isopph), or aniline (Hisoanil). The following complexes have been synthesized: [(isoaph)Cu]4, (Hisoaph)2Co, (Hisopph)2 M·nH2O (M=Ni(II), n=2;M=Pd(II), n=0;M=Co(II), n=2), [(isopph) Cu·H2O]2, and (isoanil)2 M (M=Ni(II), Cu(II), Co(II), or Pd(II)). Both chelate rings in these metal complexes are five-membered. Transimination of one –C=N–C6H5 group to –C=NH in (isoanil)2Ni produced a six-membered chelate ring in (isoim)Ni(isoanil). The induced chelate isomerism is ascribed to intermolecular hydrogen bonding of the imino-hydrogen and the basic nitrogen of the same six-membered chelate ring of an adjacent square planar molecule. Other types of hydrogen bondings with the oximato oxygen (intra- or intermolecular) favour the formation of five-membered chelate rings. Analytical, spectroscopic, and magnetic moment data are in accordance with the suggested formulations.Part of the Ph.D. thesis of Sana M. Imam  相似文献   

6.
Summary N-(o-hydroxybenzylidene)-2-aminobenzimidazole (HL) andN-(o-hydroxybenzylidene)-2(2-aminophenyl)benzimidazole (HL) react with CoX2 (X=Cl, Br, or NCS) and FeCl3 yielding complexes of general formulae [Co(HL)2X2], [Co(HL)2X2], [FeCl2(HL)2] [FeCl4], and [FeCl2(HL)2][FeCl4]. Moreover, it was possible to isolate the complexes [Co(HL)Br2] [Co(L)Cl] and [Co(L)Cl]. The complexes were characterized by elemental analyses, i.r. and electronic spectroscopies and conductivity and magnetic measurements at different temperatures.  相似文献   

7.
Novel optical ligands bis(menthane) (H2L1), pinano-para-menthane (H2L2), and carano-para-menthane (H2L3) propylenediaminodioximes are obtained. Diamagentic Co(III) complexes of the composition Co(HL1)Cl2 (I), Co(HL2)Cl2 (II), Co(HL3)Cl2 (III), and Co(HL4)Cl2 · H2O(IV) are synthesized by reactions of CoCl2 with H2L1, H2L2, H2L3 and bis(carane) propylenediaminodioxime (H2L4) in ethanol in air. The crystal and molecular structures of compound I is determined by X-ray diffraction analysis. The crystals are monoclinic with the unit cell parameters a = 7.8385(3) Å, b = 11.4074(6) Å, c = 14.9509(6) Å, β = 104.278(2)°, V = 1295.57(10) Å3, Z = 2, ρ(calcd) = 1.367 g/cm3, F(000) = 564, M = 533.41, space group P21. The crystal structure of complex I consists of individual mononuclear molecules. The Co3+ ion coordinates four N atoms of tetradentate cycle-forming anionic ligand and two Cl atoms. The coordination polyhedron of Cl2N4 is a distorted octahedron. The 13C and 1H NMR spectra of the complexes synthesized confirm coordination of four N atoms of a ligand.  相似文献   

8.
Four new nickel(II), zinc(II), and cobalt(II) complexes, [Zn(L1)2]?·?H2O (1), [Ni(L1)2]?·?H2O (2), [Ni(L2)2] (3), and [Co(L3)2]?·?H2O (4), derived from hydroxy-rich Schiff bases 2-{[1-(5-chloro-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL1), 2-{[1-(2-hydroxy-3-methoxyphenyl)methylidene]amino}-2-ethylpropane-1,3-diol (HL2), and 2-{[1-(5-bromo-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL3) have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray determination. Each metal in the complexes is six-coordinate in a distorted octahedral coordination. The Schiff bases coordinate to the metal atoms through the imino N, phenolate O, and one hydroxyl O. In the crystal structures of HL1 and the complexes, molecules are linked through intermolecular O–H···O hydrogen bonds, forming 1-D chains. The urease inhibitory activities of the compounds were evaluated and molecular docking study of the compounds with the Helicobacter pylori urease was performed.  相似文献   

9.
Complexation of N-(2-pyridyl)methyl-3-aminopropionic (HL1) and N-(2-pyridyl)methyliminodipropionic (H2L2) acids with copper(II), nickel(II), and cobalt(II) ions is studied. The composition of complexes is determined using the Starik–Barbanel relative yield method. The acid dissociation constants of HL1 and H2L2 are determined potentiometrically; the stability constants of HL1 and H2L2 complexes with metal ions are calculated.  相似文献   

10.
Summary Acetylacetone bis-benzoylhydrazone (PhCONHN=CMe)2 CH2(LH2) and acetylacetone bis-isonicotinoylhydrazone (NC5H4CONHN=CMe)2CH2(LH2) complexes of the types [ML] and [ML] (M = CoII, NiII, CuII or ZnII) have been prepared and characterized. All the complexes are non-electrolytes and the cobalt(II) complexes are lowspin, the nickel(II) complexes are diamagnetic and the copper(II) complexes are paramagnetic. The ligands chelate via two C=N groups and two deprotonated enolate groups. The e.s.r. spectra of the copper(II) complexes indicate a tetragonally distorted dimeric structure. The X-ray diffraction parameters for [CoL] and [NiL] correspond to a tetragonal crystal lattice.  相似文献   

11.
Summary Complexes of nickel(II), palladium(II), copper(II), cobalt(II), and cobalt(III) with methyl-2-(-salicylaldiminoethyl)-cyclopent-1-en-dithiocarboxylate (H2L1) and methyl-2-(-salicylaldiminoisopropyl)cyclopent-1-en-dithiocarboxylate (H2L2) have been prepared. They contain the donor sites ONNS. The metal(II) ions from neutral, monomeric square planar chelate complexes. The cobalt(III) complexes [CoL1-(H2O)2]X (X=Cl or ClO4) appear to betrans-diaqua-species. All compounds have been characterized by a number of physico-chemical methods.  相似文献   

12.
Synthesis of four different types of ligands Ar[COC(NOH)R] n (Ar = biphenyl, n = 1, HL1; Ar = biphenyl, n = 2, H2L2; Ar = diphenylmethane, n = 1, HL3; Ar = diphenylmethane, n = 2, H2L4; R = furfurylamine in all ligands) and their dinuclear Co2+, Ni2+, Cu2+, and Zn2+ complexes is reported herein. These compounds were characterized by elemental analysis, ICP-OES, FT-IR spectra, and magnetic susceptibility measurements. The ligands were further characterized by 1H NMR. The results suggest that dinuclear complexes of HL1 and HL3 have a metal to ligand mole ratio of 2: 2 and dinuclear complexes H2L2 and H2L4 have a metal to ligand mole ratio of 2: 1. Square pyramidal or octahedral structures are proposed for complexes of oxime ligands. Furthermore, extraction abilities of the four ligands were also evaluated in chloroform using selected transition metal picrates such as Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pb2+. The ligands show strong binding ability towards Hg2+ and Cu2+ ions.  相似文献   

13.
Heteronuclear complexes containing oxorhenium(V), with Fe(III), Co(II), Ni(II), Cu(II), Cd(II) and UO2(VI) ions were prepared by the reaction of the complex ligands [ReO(HL1)(PPh3)(OH2)Cl]Cl (a) and/or [ReO(H2L2)(PPh3)(OH2)Cl]Cl (b), where H2L1?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(5,6-diphenyl-1,2,4-triazine-3-ylhydrazone) and H3L2?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(1H-benzimidazol-2-ylhydrazone), with transition and actinide salts. Heterodinuclear complexes of ReO(V) with Fe(III), Co(II), Ni(II), Cu(II) and Cd(II) were obtained using a 1?:?1 mole ratio of the complex ligand and the metal salt. Heterotrinuclear complexes were obtained containing ReO(V) with UO2(VI) and Cu(II) using 2?:?1 mole ratios of the complex ligand and the metal salts. The complex ligands a and b coordinate with the heterometal ion via a nitrogen of the heterocyclic ring and the nitrogen atom of the C=N7 group. All transition metal cations in the heteronuclear complexes have octahedral configurations, while UO2(VI)?complexes have distorted dodecahedral geometry. The structures of the complexes were elucidated by IR, ESR, electronic and 1H NMR spectra, magnetic moments, conductance and TG-DSC measurements. The antifungal activities of the complex ligands and their heteronuclear complexes towards Alternaria alternata and Aspergillus niger showed comparable behavior with some well-known antibiotics.  相似文献   

14.
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   

15.
Complexes of N-phthaloylglycinate (N-phthgly) and CoII, NiII, CuII, ZnII and CdII containing imidazole (imi), N-methylimidazole (mimi), 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen), and tridentate amines such as 2,2,2-terpyridine (terpy) and 2,4,6-(2-pyridyl)s-triazine (tptz), were prepared and characterized by conventional methods, i.r. spectra and by thermogravimetric analysis. For imi and mimi ternary complexes, the general formula [M(imi/mimi)2(N-phthgly)2nH2O, where M = CoII, NiII, CuII and ZnII applies. For CdII ternary complexes with imi, [Cd(imi)3(N-phthgly)2]·2H2O applies. For the bi and tridentate ligands, ternary complexes of the formula [M(L)(N-phthgly)2nH2O were obtained, where M = CoII, NiII, CuII and ZnII; L = bipy, phen, tptz and terpy. In all complexes, N-phthgly acts as a monodentate ligand, coordinating metal ions through the carboxylate oxygen, except for the ternary complexes of CoII, NiII and CuII with mimi and CuII and ZnII with imi, where the N-phthgly acts as a bidentate ligand, coordinating the metal ions through both carboxylate oxygen atoms.  相似文献   

16.
Reactions of Ni(NO3)2 · 6H2O) in EtOH(iso-PrOH) with optically active bis(menthane) ethylene-diaminodioxime (H2L1), pinano-para-menthane ethylenediaminodioxime (H2L2), pinano-para-menthane propylenediaminodioxime (H2L3) and bis(pinane) propylenediaminodioxime (H2L4) were used to synthesize [Ni(H2L1)NO3[NO3 · 2H2O (I), [Ni(HL2)]NO3 (II), [Ni(HL3)]NO3 (III), and [Ni(HL4)]NO3 (IV). X-ray diffraction study of paramagnetic complex Ieff = 3.04 μB and diamagnetic complexes II and III revealed their ionic structures. A distorted octahedral polyhedron N4O2 in the cation of complex I is formed by the N atoms of tetradentate cycle-forming ligand, i.e., the H2L1 molecule, and the O atoms of the NO 3 ? anion acting as a bidentate cyclic ligand. In the cations of complexes II and III, containing a pinane fragment, the coordination core NiN4 has the shape of a distorted square formed on coordination of tetradentate cycle-forming ligands, i.e., anions of the starting dioximes. The structure of diamagnetic complex IV is likely to be similar to the structures of complexes II and III.  相似文献   

17.
Vicinal carbonyl oxime (HL1) and oxime-imine (H2L2) ligands and their mononuclear Ru(III) and Cu(II), heterodinuclear Ru(III)-Mn(II), Ru(III)-Ni(II), Ru(III)-Cu(II), and heterotrinuclear Ru(III)-Cu(II)-Ru(III) chelates were synthesized and characterized by elemental analysis, molar conductivity, IR, ESR, ICP-OES, magnetic moment measurements, and thermal analyses studies. The free ligands were also characterized by 1H NMR spectra. The carbonyl-oxime ligand coordinates through the oxygen of =N-OH to form a six-membered chelate ring. The quadridentate tetraaza ligand (H2L2) obtained by condensing of the bidentate ligand 1-p-diphenylmethane-2-hydroxyimino-2-(1-naphthylamino)-1-ethanone (HL1) with 1,2-phenylenediamine coordinates with Ru(III) through its nitrogen donors in the equatorial position with the loss of one of the oxime protons and concomitant formation of an intramolecular hydrogen bond. Stoichiometric and spectral results of the metal complexes indicated that the metal: ligand ratios in the mononuclear complexes of the ligand (HL1) were found to be 1: 2, while these ratios were 1: 1 in the mononuclear complexes of the ligand (H2L2). The metal: ligand ratios of the dinuclear complexes were found to be 2: 1, and this ratio was 3: 2 in the trinuclear complex. The article is published in the original.  相似文献   

18.
Nickel(II) complexes of quinoline-2-carbaldehyde N(4),N(4)-(butane-1,4-diyl) thiosemicarbazone (HL1) and 2-benzoylpyridine N(4),N(4)-(butane-1,4-diyl) thiosemicarbazone (HL2) have been synthesized and physico-chemically characterized by means of partial elemental analyses, molar conductance measurements, magnetic measurements, electronic and infrared spectral studies. Three complexes were given the formulae [Ni(HL1)2]Cl2 (1), [Ni(HL2)L2]ClO4 · 7H2O (2) and [NiL2Cl] · 0.5H2O (3). The structure of compound 1 has been solved by single crystal X-ray crystallography and is found to be distorted octahedral. Compound 2, when crystallized in DMSO solution, got deprotonated to form a new compound [Ni(L2)2] (2a), with a distorted octahedral Ni(II) center. In compound 1, HL1 coordinates to the metal in the thione form, while in compounds 2a and 3, HL2 coordinates in its deprotonated thiolate form.  相似文献   

19.
Summary FeIII complexes have been prepared from the dihydroxamic acids (CH2)n[CON(R)OH]2 (n=2, 3, 4, 6, 8; R=H, Ph,o-tolyl,p-tolyl) (H2L) and the amino monohydroxamic acids H2NCH(R)CONHOH (R=H, Me) (HL) and XC6H4CONHOH (X=o-NH2,p-NH2) (HL). Based on elemental analyses, molecular weight data, and electronic and i.r. spectra, the complexes have been formulated as Fe2(LH)2L2, Fe2L2O and Fe2L3 for the dihydroxamic acids, and Fe(OH)4L2(H2O)2 and FeL3 for the amino monohydroxamic acids. The57Fe Mossbauer spectra are discussed.The author is née Bose  相似文献   

20.
A novel series of thiourea derivatives, namely, N,N-diphenyl-N-(4-phenyl-benzoyl)thiourea (HL1), N,N-diphenyl-N-(4-chloro-benzoyl)thiourea (HL2) and N,N-di-n-propyl-N-(4-chloro-benzoyl)thiourea (HL3), and its metal complexes has been prepared and characterised by elemental analysis, i.r. spectroscopy, 1H-n.m.r. spectroscopy, mass spectrometry and single crystal X-ray diffraction. The ligand coordinates to NiII, CuII and CoII in a bidentate manner yielding essentially neutral complexes of the type cis-[ML2]. N.m.r. spectra and single crystal X-ray diffraction analysis revealed the presence of a distorted tetrahedral coordination ML2 complex.  相似文献   

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