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1.
New bidentate Schiff-base ligands 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarbothioamide HL1 and 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarboxamide HL2 were synthesized from the condensation of 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one with thiosemicarbazide and semicarbazide, respectively. Homoleptic complexes of these ligands, of general formula K[Cr(L n )2Cl2], K2[Mn(L n )2Cl2], K2[Fe(L1)2Cl2] and [M(L n )2] (where M = Co(II), Ni(II) Cu(II), Zn(II), Cd(II), and Hg(II) ions; n = 1 or 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometry for Cr(III), Mn(II), and Fe(II) complexes, square planar for Cu(II), Co(II), and Ni(II) complexes and tetrahedral for Zn(II), Cd(II), and Hg(II) complexes.  相似文献   

2.
New Mannich bases bis(thiosemicarbazide methyl) phosphinic acid H3L1 and bis(1-phenylsemicarbazide methyl) phosphinic acid H3L2 were synthesized from condensation of phosphinic acid and formaldehyde with thiosemicarbazide and 1-phenylsemicarbazide, respectively. Monomeric complexes of these ligands, of general formula K2[CrIII(L n )Cl2], K3[FeII(L1)Cl2], K3[MnII(L2)Cl2], and K[M(L n )] (M = Co(II), Ni(II), Cu(II), Zn(II) or Cd(II); n = 1, 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR, and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometries for the Cr(III), Mn(II), and Fe(II) complexes, square planar for Co(II), Ni(II), and Cu(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes. Complex formation via molar ratio in DMF solution has been investigated and results were consistent to those found in the solid complexes with a ratio of (M : L) as (1 : 1).  相似文献   

3.
The new Mannich bases bis(1,4-diphenylthiosemicarbazide methyl) phosphinic acid H3L1 and bis(1,4-diphenylsemicarbazide methyl) phosphinic acid H3L2 were synthesised from the condensation of phosphinic acid, formaldehyde with 1,4-diphenyl thiosemicarbazide and 1,4-diphenylsemicarbazide, respectively. Monomeric complexes of these ligands, of general formulae K2[CrIII(L n )Cl2], K3[MnII(L n )Cl2] and K[M(L n )] (M = Co(II), Ni(II), Cu(II), Zn(II) or Hg(II); n = 1, 2), are reported. The mode of bonding and overall geometry of the complexes were determined through physico-chemical and spectroscopic methods. These studies revealed octahedral geometries for the Cr(III), Mn(II) complexes, square planar for Co(II), Ni(II) and Cu(II) complexes and tetrahedral for the Zn(II) and Hg(II) complexes.  相似文献   

4.

Two novel asymmetrical Schiff-base ligands, H2L1 and H2L2, were prepared by reacting two half-unit Schiff-base compounds with 2-methyl-7-formyl-8-hydroxyquinoline. The two half-unit Schiff-base compounds were initially prepared by condensing dimedone with either ethylenediamine or p-phenylenediamine, respectively. Both ligands are dibasic and contain two sets of NO coordinating sites. Twelve metal complexes were obtained by reacting both ligands with Cu(II), Ni(II), Co(II), Mn(II), Fe(III), VO(IV) cations. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis, ESR and mass spectra, also magnetic moments of the complexes were determined. Visible spectra of the complexes indicated distorted octahedral geometries around the metal cations. ESR spectra indicated mononuclear and dinuclear structures of the complexes of ligands H2L1 and H2L2, respectively. Magnetic moments of the complexes were rather low compared with those expected for octahedral geometries and indicated polymeric linkage of the metal complex molecules within their crystal lattices. The insolubility of the metal complexes in most organic solvents support the polymeric structures.  相似文献   

5.
Reactions of 3-acetyl-2,5-dimethylthiophene with thiosemicarbazide and semicarbazide hydrochloride resulted in the formation of new heterocyclic ketimines, 3-acetyl-2,5-dimethylthiophene thiosemicarbazone (C9H13N3OS2 or L1H) and 3-acetyl-2,5- dimethylthiophene semicarbazone (C9H13N3OS or L2H), respectively. The Pd(II) and Pt(II) complexes have been synthesized by mixing metal salts in 1:2 molar ratios with these ligands by using microwave as well as conventional heating method for comparison purposes. The authenticity of these ligands and their complexes has been established on the basis of elemental analysis, melting point determinations, molecular weight determinations, IR, 1H NMR and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a monobasic bidentate manner and square planar environment around the metal atoms has been proposed to the complexes. Both the ligands and their complexes have been screened for their antimicrobial activities. The antiamoebic activity of both the ligands and their palladium compounds against the protozoan parasite Entamoeba histolytica has been tested.  相似文献   

6.
The potassium salt of salicylidene-DL-alanine (KHL), bis(benzylidene)ethylenediamine (A1), thiophene-o-carboxaldene-p-toluidine (A2), and its metal complexes of the formula [(MII(L)(A)(H2O)] (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II); A = A1 or A2) are prepared. They are characterized by elemental analysis, magnetic susceptibility measurements, thermogravimetric analysis, and infrared and electronic spectral studies. The electronic spectral and magnetic moment data suggest an octahedral geometry for the complexes. All of these complexes, metal nitrates, fungicides (bavistin and emcarb), and ligands are screened for their antifungal activity against Aspergillus niger, Fusarium oxysporum, and Aspergillus flavus using a plate poison technique. The complexes show higher activity than those of the free ligands, metal nitrate, and the control (DMSO) and moderate activity against bavistin and emcarb. The text was submitted by the authors in English.  相似文献   

7.
Cobalt(II) and copper(II) complexes with three dioxime ligands cyclohexylamine-p-tolylglyoxime (L1H2), tert-butyl amine-p-tolylglioxime (L2H2) and sec-butylamine-p-tolylglyoxime (L3H2), have been prepared. The metal to ligand ratios of the complexes were found to be 1?:?2. The Cu(II) complexes of these ligands are proposed to be square planar; the Co(II) complexes are proposed to be octahedral with water molecules as axial ligands. Ligands and complexes are soluble in common solvents such as DMSO, DMF, CHCl3 and C2H5OH. The ligands have been characterized by elemental analysis, IR, UV-VIS, 1H?NMR, 13C?NMR and thermogravimetric analysis (TGA). The complexes were characterized by elemental analysis, IR, UV-VIS, magnetic susceptibility measurements, thermogravimetric analysis (TGA) and electrochemistry. Electrochemical properties of metal complexes show quasi-reversible one-electron redox processes. However, Co(L1H)2 and Cu(L1H)2 complexes show another oxidation peak in the positive region. This single irreversible oxidation peak is caused by the cyclic ring of the ligand. Data also revealed that the electron transfer rates of metal complexes with L1H2 are higher than the other complexes.  相似文献   

8.
Two bidentate Schiff bases, 5-methyl-2-p-tolyl-4-(1-p-tolylimino-propyl)-2H-pyrazol-3-ol (L1) and 2-(3-chloro-phenyl)-5-methyl-4-(1-p-tolylimino-propyl)-2H-pyrazol-3-ol (L2), were synthesized by condensation of 4-acyl pyrazolones with p-toluidine in ethanol. These ligands have been characterized by elemental analysis, infrared (IR), 1H NMR, and mass spectra. A single crystal molecular structure of ligand L2 was also solved. Nickel(II) complexes of these ligands with general formula [ML2?·?2H2O] have been prepared by the interaction of aqueous solution of Ni-acetate with ethanolic solution of the appropriate ligand. The complexes were separated, analyzed, and their structures were elucidated on the basis of elemental analysis, Ni(II) determination, IR, UV-Vis, conductance, mass, and TGA-DTA data. Octahedral structure was proposed for the synthesized complexes.  相似文献   

9.
Two new soluble vic-dioxime ligands, 4-isopropylanilineglyoxime (L1H2) and 4-benzylpiperidineglyoxime (L2H2) were prepared by reacting 4-isopropylaniline and 4-benzylpiperidine with anti-chloroglyoxime. Ten metal complexes were obtanied by reacting both ligands with Cu(II),Ni(II),Co(II), Zn(II), and Cd(II) cations. The ligands and their metal complexes were elucidated by elemental analysis, IR, UV-vis, 1H NMR, and 13C NMR and also magnetic moments of the complexes were determined. The text was submitted by the authors in English.  相似文献   

10.
Synthesis and spectroscopic characterization of Schiff-base complexes of Cu(II), Ni(II), and Mn(II) resulting from condensation of salicylaldehyde derivatives with thiosemicarbazide [PHBT = 1-(5-(2-phenyldiazenyl)-2-hydroxybenzylidene)thiosemicarbazide, CHBT = 1-(5-(2-(2-chlorophenyl)diazenyl)-2-hydroxybenzylidene)thiosemicarbazide, and MHBT = 1-(5-(2-p-tolyldiazenyl)-2-hydroxybenzylidene)thiosemicarbazide] are discussed. The solid complexes were confirmed by elemental analysis (CHN), molar conductance, and mass spectra. Important infrared (IR) spectral bands corresponding to the active groups in the three ligands, 1H-NMR and UV-Vis spectra and thermogravimetric analysis were performed. The dehydration and decomposition of [Cu(PHBT)(H2O)], [Ni(PHBT)(H2O)] · 2H2O, [Mn(PHBT)(H2O)] · H2O, [Cu(CHBT)(H2O)], [Ni(CHBT)(H2O)] · H2O, [Mn(CHBT)(H2O)] · H2O, [Cu(MHBT)(H2O)], [Ni(MHBT)(H2O)] · 2H2O, and [Mn(MHBT)(H2O)] · 2H2O complexes were studied. The ligands are tridentate forming chelates with 1 : 1 (metal : ligand) stoichiometry. The molar conductance measurements of the complexes in DMSO indicate non-electrolytes. The biological activities of the metal complexes have been studied against different gram positive and gram negative bacteria.  相似文献   

11.
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   

12.
Reaction of dibutyltin dichloride, dimethyltin dichloride, and tributyltin chloride with ligands derived from thiosemicarbazone and semicarbazone leads to the formation of a new series of organotin(IV) complexes of general formula R2SnCl2·L and R3SnCl·L (where L ligands derived from the condensation of thiosemicarbazide and semicarbazide with 4-hydroxy-3-methoxybenzaldehyde). The authenticity of these ligands and their metal complexes have been established on the basis of elemental analysis, conductance measurements, molecular weight determinations, infrared, 1H NMR, 13C NMR, 119Sn NMR, and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a bidentate. An octahedral structure is proposed for the organotin(IV) complexes. The ligands and its metal complexes are screened for their antimicrobial activities against some Gram-positive and Gram-negative bacteria, and fungus. The studies demonstrated that metalation can increase the antimicrobial activity rather than the free ligands.  相似文献   

13.
Three novel ligands, a-pycolyliminoisonitrosoacetophenone (L1H · HCl), α-pycolylimino-p-methylisonitrosoacetophenone (L2H · HCl), and a-pycolylimino-p-chloroisonitrosoacetophenone L3H, were synthesized. Their metal complexes with Co(II), Cu(II), and Ni(II) were prepared. The mononuclear complexes of these ligands with Co2+, Cu2+, and Ni2+ ions were obtained in ethanol. The structures of the ligands and their complexes were characterized by 1H NMR, IR spectroscopy, elemental analyses, and magnetic susceptibility. The text was submitted by the authrs in English.  相似文献   

14.
Two new series of copper(II), nickel(II), cobalt(II), zinc(II), iron(III), chromium(III), vanadyl(IV) and uranyl(VI) complexes with two bifunctional tridentate Schiff base, H4L1 and H2L2 ligands have been prepared. The Schiff base, H4L1 and H2L2, ligands were synthesized by the condensation of 4,6-diacetylresorcinol with o-aminophenol or o-phenylenediamine. The ligands are either di- or tetra-basic with two symmetrical sets of either OON or NNO tridentate chelating sites. The ligands and their metal complexes have been characterized by elemental analysis, 1H-n.m.r., FT-IR, mass, electronic, esr spectra and thermal gravimetric analysis and magnetic susceptibility. With the exception of CoII ion with H2L2 which afforded a trinuclear complex, a variety of binuclear complexes for the rest of the metal complexes were obtained with the ligands in its di- or tetra-deprotonated forms. The bonding sites are the azomethine and amino nitrogen atoms, and phenolic oxygen atoms. The metal complexes exhibit different geometrical arrangements such as square planar, tetrahedral, square pyramid and octahedral arrangement.  相似文献   

15.
Thiosemicarbazides and their metal complexes have attracted considerable interest because of their biological activities and their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Discrete copper(II) and cadmium(II) complexes have been prepared by crystallization of N‐[2‐(2‐hydroxybenzoyl)hydrazinecarbonothioyl]propanamide (H3L) with Cu(CH3COO)2 or Cd(NO3)2 in a dimethylformamide/methanol mixed‐solvent system at room temperature, affording the complexes di‐μ‐acetato‐bis{μ4‐1‐[(2‐oxidophenyl)carbonyl]‐2‐(propanamidomethanethioyl)hydrazine‐1,2‐diido}tetracopper(II) dimethylformamide disolvate, [Cu4(C11H10N3O3S)2(C2H3O2)2]·2C3H7NO, (I), and bis{μ2‐[(2‐hydroxyphenyl)formamido](propanamidomethanethioyl)azanido}bis[(4,4′‐bipyridine)nitratocadmium(II)] dihydrate, [Cd2(C11H12N3O3S)2(NO3)2(C10H8N2)2]·2H2O, (II). Complex (I) consists of four CuII cations, two μ4‐bridging trianionic ligands and two μ2‐bridging acetate ligands, while complex (II) is composed of two CdII cations, two μ2‐bridging monoanionic ligands, two nitrate ligands and two 4,4′‐bipyridine ligands. These discrete complexes are connected by hydrogen bonds and van der Waals interactions to form a three‐dimensional supramolecular architecture. Compared with (I), the phenolic hydroxy group and hydrazide N atom of the thiosemicarbazide ligand of (II) are not involved in coordination and lead to a binuclear CdII complex. This different coordination mode may be attributed to the larger ionic radius of the CdII ion compared with the CuII ion.  相似文献   

16.
Solid complexes of Pb(II) with unsymmetrical Schiff-base ligands (H2L) derived from 2-aminobenzophenone, thiosemicarbazide, semicarbazide, salicylaldehyde, 2-hydroxynaphthaldehyde, and o-hydroxyacetophenone have been synthesized and characterized by elemental analysis, conductance measurements, molecular weight measurement, and UV–Vis, FTIR, 1H NMR, and 13C NMR spectroscopy. The spectral studies suggest the ligands behave as dibasic tetradentate ligands with ONNO/ONNS donor atom sequences toward the central metal ion. From the microanalytical data, the stoichiometry of the complexes was found to be 1:1 (metal:ligand). The physicochemical data suggest a tetracoordinated environment around the metal ion. Three-dimensional molecular modeling and analysis of bond lengths and bond angles have also been conducted for a representative compound, [PbL1], to substantiate the proposed structures.  相似文献   

17.
Complexes of two series of Schiff base ligands, H2La and H2Lbderived from the reaction of 2,6-diacetyl pyridine with semicarbazide, H2La and thiosemicarbazide, H2Lb, with the metal ions, Co(II), Ni(II), Cu(II), VO(IV) and UO2(VI) have been prepared. The ligands are characterized by elemental analysis, IR, UV–vis and 1H NMR. The structures of the complexes are investigated with the IR, UV–vis, X-band ESR spectra, 1H NMR and thermal gravimetric analysis as well as conductivity and magnetic moment measurements. The IR-spectra reveal the presence of variable modes of chelation for the investigated ligands. A variety of binuclear or mononuclear complexes were obtained with the two ligands in tri-, tetra or pentadentate forms. The bonding sites are the pyridine nitrogen, two azomethine nitrogen atoms and ketonic oxygen in case of H2La or sulphur atoms in case of H2Lb. The Coats–Redfern equation has been used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. Cyclic voltammograms of Co(II) and Ni(II) show quasi-reversible peaks. The redox properties and the nature of the electro-active species of the complexes have been characterized.  相似文献   

18.
Co(II), Ni(II), Cu(II), and Zn(II) complexes have been prepared with Schiff bases derived from 3-formyl-2-mercaptoquinoline and substituted anilines. The prepared Schiff bases and chelates have been characterized by elemental analysis, molar conductance, magnetic susceptibilities, electronic, IR, 1H-NMR, ESR, cyclic voltammetry, FAB-mass, and thermal studies. The complexes have stoichiometry of the type ML2 · 2H2O coordinating through azomethine nitrogen and thiolate sulfur of 2-mercapto quinoline. An enhancement in fluorescence has been noticed in the Zn(II) complexes whereas quenching occurred in the other complexes. The ligands and their metal complexes have been screened in vitro for antibacterial and antifungal activities by MIC methods with biological activity increasing on complexation. Cu(II) complexes show greater bacterial than fungicidal activities. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties of the ligands and their corresponding complexes. Only four compounds have exhibited potent cytotoxic activity against Artemia salina; the other compounds were almost inactive for this assay.  相似文献   

19.
Mn(II), Co(II), Ni(II) and Cu(II) complexes have been synthesized with 22 and 24 membered tetramide macrocyclic ligands viz; 1,9,12,20-tetraaza-2,8,13,19-tetraone-5,16-dithiacyclodocosane [L1] and 1,9,13,21-tetraaza-2,8,14,20-tetraone-5,17-dithiacyclotetracosane [L2] and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic EPR spectral studies and electrochemical properties. The molar conductance of all the complexes in DMSO solution is corresponding to 1:2 electrolyte. Thus these complexes may be formulated as [M(L′)]Cl2 [where M = Mn(II), Co(II), Ni(II) and Cu(II) L′ = L1 and L2]. On the basis of spectral studies a distorted octahedral geometry has been assigned for all the complexes. The ligands and their complexes were also screened in vitro against two pathogenic fungi (F. moniliformae and R. solani) to assess their growth inhibiting potential.  相似文献   

20.
A new series of antibacterial and antifungal amino acid derived Schiff bases and their cobalt(II), copper(II), nickel(II) and zinc(II) metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, IR and electronic spectral measurements. The spectral data indicated the Schiff base ligands ( L 1– L 5) derived by condensation of salicylaldehyde with glycine, alanine, phenylalanine, methionine and cysteine, to act as tridentate towards divalent metal ions (cobalt, copper, nickel and zinc) via the azomethine‐N, deprotonated carboxyl group of the respective amino acid and deprotonated oxygen atom of salicylaldehyde by a stoichiometric reaction of M: L (1:2) to form complexes of the type K2[M( L )2] [where M = Co(II), Cu(II), Ni(II) and Zn(II)]. The magnetic moments and electronic spectral data suggested that all complexes have an octahedral geometry. Elemental analyses and NMR spectral data of the ligands and their Zn (II) complexes agree with their proposed structures. The synthesized ligands, along with their metal complexes, were screened for their in‐vitro antibacterial activity against four Gram‐negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa and Salmonella typhi) and two Gram ‐ positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and for in‐vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glaberata. The results of these studies show the metal complexes to be more antibacterial/antifungal against one or more species as compared with the uncomplexed Schiff base ligands. The brine shrimp bioassay was also carried out to study their in‐vitro cytotoxic properties. Only three compounds ( 2, 11 and 17 ) displayed potent cytotoxic activity as LD50 = 8.196 × 10?4, 7.315 × 10?4 and 5.599 × 10?4 M /ml respectively, against Artemia salina. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

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