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1.
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   

2.
Two new Schiff base ligands containing 2,4–disubstituted thiazoles and cyclobutane rings, 4-(1-methyl-1-phenylcyclobutane-3-yl)-2-(2-hydroxy-3-methoxybenzylidenehydrazino)thiazole (L1H), 4-(1-methyl-1-p-xylylcyclobutane-3-yl)-2-(2-hydroxy-3-methoxybenzylidenehydrazino)thiazole (L2H) and their mononuclear complexes with a 1:2 metal–ligand ratio have been prepared from acetate salts of CoII, CuII, NiII and ZnII in EtOH. The authenticity of the ligands and their complexes have been established by microanalyses, i.r., 13C- and 1H-n.m.r. spectra, and by magnetic susceptibility and conductivity measurements. The complexes are mononuclear. Thermal properties of the ligands and complexes have been studied by t.g.a. and d.s.c. techniques. Antimicrobial activities of the ligands and their complexes have been tested against six different microorganisms; three are yeast and three are bacteria. One of the ligands and many of the complexes were found to be active against some of the microorganisms studied.  相似文献   

3.
A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2-octylsulfanylaminobenzene and (E,E)-dichloroglyoxime. Mononuclear transition metal complexes of NiII, CuII, CoII and FeII have been prepared and were found to have a metal–ligand ratio of 1:2. The synthesis of di- and trinuclear complexes was achieved with UIVO2 and CuII depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.–vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.  相似文献   

4.
A new ligand, 5-nitrosalicylidene-p-aminoacetophenoneoxime (HL), was synthesized from p-aminoacetophenoneoxime and 5-nitrosalicylaldehyde under reflux in absolute EtOH at 60°C for 3 h. Mononuclear complexes with a metal : ligand ratio of 1 : 2 were prepared with CoII, NiII,CuII, and ZnII salts. Their structures were determined on the basis of elemental analyses, IR, 1H and 13C NMR, electronic spectra, magnetic susceptibility measurements, molar conductivity, and thermogravimetric analyses. According to the results, two ligands were suggested to be coordinated to each metal atom by phenolic oxygen and imino nitrogen to form high-spin tetrahedral complexes with cobalt(II), nickel(II), and copper(II) while forming a diamagnetic complex with zinc(II).__________From Koordinatsionnaya Khimiya, Vol. 31, No. 6, 2005, pp. 441–445.Original English Text Copyright © 2005 by Canpolat, Kaya.This article was submitted by the authors in English.  相似文献   

5.
Complexing processes in MII-N-diisopropoxythiophosphorylthiobenzamide binary systems (M = Co, Ni, Cu) in metal(II) hexacyanoferrate(II) gelatin-immobilized matrices upon contact with aqueous–alkaline (pH = 12.0 ± 0.1) solutions of organic compounds have been studied. It has been shown that, in CoII and CuII, the initial act of complexing involves destruction of the CoII and CuII hexacyanoferrates(II) by OH ions, leading to formation of the corresponding hydroxides which react with the ligand indicated. In the both systems, successive addition of two ligand molecules per M(OH)2 fragment occurs and [MB(OH)(OH2)] and [MB2] coordination compounds are formed (B-a singly deprotonated ligand form). In the NiII-N-diisopropoxythiophosphorylthiobenzamide system, the formation of three complexes, (Ni2BOH)2[Fe(CN)6], [NiB(OH)(OH2)] and [NiB2] occurs.  相似文献   

6.
New mixed ligand complexes of benzoyldithiocarbazate (H2BDT) have been synthesized and characterized by elemental analyses, spectral studies (i.r., u.v.–vis., mass), thermal analysis and electrical conductivity measurements. The complexes have the general formulae: [M2(BDT)(OX)2] · xH2O; [Co2(BDT)(OX)2(H2O)4]; [M(HBDT)(OX)-(H2O)], [Ni(BDT)(py)2] n and [Ni(BDT)(L)] n where M = MnII, NiII and CuII; BDT = dithiocarbazate dianion; OX = 8-hydroxyquinolinate; x = 1 or 2; M = ZnII or CdII; HBDT = dithiocarbazate anion and L = 2,2-bipyridyl or 1,10-o-phenanthroline. For the [M2(BDT)(OX)2] · xH2O, [Co2(BDT)(OX)2(H2O)4], [Ni(BDT)(py)2] n and [Ni(BDT)(L)] n complexes, benzoyldithiocarbazate acts as a dibasic-tetradentate ligand in the enol form via the enolic oxygen, the hydrazide nitrogens and the thiolate sulphur, while it acts as a monobasic-tridentate ligand in the keto form in the [M(HBDT)(OX)(H2O)] complexes. The thermal behaviour of the complexes has been studied by t.g.–d.t.g. techniques. Kinetic parameters of the thermal decomposition process have been computed by Coats–Redfern and Horowitz–Metzger methods. It is obvious that the thermal decomposition in the complexes occurs directly at the metal–ligand bonds except for the ZnII and CdII complexes in which decomposition seems to be at a point in the benzoyldithiocarbazate moiety. From the calculated kinetic data it can be concluded that the dehydration processes in all complexes have been described as phase-boundary controlled reactions. The activation energy values reveal that the thermal stabilities of the homobimetallic complexes lie in the order: MnII < NiII < CoII, while the monomeric CdII complex has more enhanced thermal stability than the ZnII complex.  相似文献   

7.
Complexes of NiII, CoII and CuII containing the macrocyclic ligand, 1,4,8,11-tetraazacyclotetradecane (cyclam), and their ability to form mixed ligand complexes with thiocyanate have been studied. These complexes in a 1:2 mole ratio, exhibit new absorption peaks at 450, 538 and 512 nm respectively. Addition of thiocyanate to the nickel–cyclam complex (1:2:5 mole ratio) led to the formation of a purple complex, exhibiting three distinct new absorption peaks at 330, 455 and 662 nm. A purple complex (1:2:10 mole ratio) separated, having absorption peaks at 352, 503 and 693 nm in CHCl3. The CoII–cyclam complex with thiocyanate in the same mole ratio exhibits two absorption peaks at 437 and 519 nm without appearance of any precipitate. The CuII–cyclam complex with thiocyanate did not form a mixed ligand complex. Electrochemical studies also confirmed the complex formation of NiII–cyclam with the thiocyanate with the appearance of two new oxidation peaks close to 1.25 and 1.60 V versus Ag/AgCl in H2O and CHCl3. The CoII–cyclam complex with thiocyanate exhibited an oxidation peak at 1.2 V versus Ag/AgCl, while no peak was observed for the CuII–cyclam complex with thiocyanate. Based on spectroscopic and electrochemical studies the geometry of the complex has been evaluated.  相似文献   

8.
Asymmetric 7-formyanil-substituted-imino-4-(4-methyl-2-butanone)-8-hydroxyquinoline-5-sulphonic acid (Schiff bases), react with CoII, NiII and CuII ions to give 1:2, 1:1 and 2:1 complexes as established by conductometric titrations in 1:1 DMF:H2O. The complexes were investigated by elemental analyses, molecular weight determinations, molar conductance, magnetic moments, thermal analysis, i.r., u.v.–vis. and e.s.r. spectra. The complexes have an octahedral crystal structure and general formula [ML·(OH2)2], where MII = Co, Ni and Cu, and L = Na[7—X—HL], (—X— = (CH2)2, (CH2)3, p-C6H4, o-C6H4). Antimicrobial activity of these new ligands and their transition metal complexes has been screened in vitro on common fungi and bacteria.  相似文献   

9.
Summary New complexes derived from polymeric N,N-o-phenylenediamine bis(cinnamaldehyde) (L) with CuII, CoII, NiII, ZnII, UO 2 II , and PdII were prepared and characterized by elemental analysis, magnetic susceptibilities and spectroscopic (IR, far-IR,1H-NMR,13C-NMR and EPR) studies. A bidentate methine nitrogen atoms coordination of the ligand is assigned in the isolated complexes. The stereochemistries of the polymer complexes have been studied with using magnetic and spectroscopic measurements. Analytical data show 2:1 or 1:1 (ligand:metal) stoichiometry with water molecules coordinated to the ZnII ion, as evidenced from IR and thermal analysis (DTA). The ligand was tested as a corrosion inhibitor for copper; the limiting concentration of the ligand to give maximum efficiency (60%) is 10–3 mol dm–3 at 25°C.
Polymere Komplexe, XXIII: Synthese und physikalisch-chemische Untersuchungen an Übergangsmetallkomplexen von symmetrischem Poly(N,N-o-phenylendiamin)bis(zimtaldehyd)
Zusammenfassung Es wurden neue Komplexe von polymerem Poly(N,N-o-phenylendiamin)bis-(zimtaldehyd) mit Cu(II), Co(II), Ni(II), Zn(II), UO2(II) und Pd(II) hergestellt und mittels Elementaranalyse, magnetischen Suszeptibilitätsmessungen und spektroskopischen Methoden (IR, far-IR,1H-NMR,13C-NMR und EPR) charakterisiert. Es wurde eine zweizähnige Methin-Stickstoff-Koordination in den Komplexen festgestellt. Die Stereochemie der Polymerkomplexe wurde mittels magnetischer und spektroskopischer Messungen untersucht. Aus den analytischen Daten, mit zusätzlichen Argumenten aus IR und thermischer Analyse (DTA), ergab sich eine 2:1 oder 1:1 (Ligand:Metall)-Stöchiometrie mit an Zn(II) koordinierten Wassermolekülen. Der Ligand wurde als Korrosionsinhibitor für Kupfer getestet: die Grenzkonzentration des Liganden zur maximalen Effizienz (60%) ist 10–3 mol dm–1 bei 25°C.
  相似文献   

10.
Summary A series of metal ion complexes of the thiosemicarbazone, 3-azabicyclo[3.2.2]nonane-3-thiocarboxylic acid 2-[1-(6-methyl-2-pyridinyl)ethylidene]hydrazide (6 MLH) have been prepared and spectrally characterized. The ligand undergoes deprotonation to coordinatevia the thione sulphur, the imine nitrogen and the pyridyl nitrogen. A single anionic ligand such as Cl, Br and NO3 completes the bonding to the CuII and NiII centre. The compound derived from CoCl2 contains two 6 MLH ligands bound to a CoII centre and a CoCl 4 2– counter ion. Complexes derived from perchlorate salts may feature 6 MLH, 6 ML, or both with the CoII being oxidized to CoIII. The solids were characterized by i.r., electronic and e.s.r. spectroscopy. In addition, electronic and e.s.r. spectra of their chloroform solutions were recorded.NATO Fellow, on leave from Istanbul Medical Faculty, Istanbul University.  相似文献   

11.
Novel terdentate neutral complexes of CuII, NiII, CoII, MnII, ZnII, CdII, HgII, VOII, ZrOII and UO2 II have been prepared using a Schiff base derived from 1-phenyl-2,3-dimethyl-4-aminopyrazol-5-one (4-aminoantipyrine) and acetoacetanilide. The structural features of the chelates have been confirmed by microanalytical data, i.r., u.v.–vis., 1H-n.m.r., e.s.r. and mass spectral techniques. Electronic absorption and i.r. spectra of the complexes indicate an octahedral geometry around the central metal ion, except for the VOII and ZrOII complexes which show square pyramidal geometry. The monomeric and neutral nature of the complexes are confirmed from their magnetic susceptibility and low conductance values. The cyclic voltammogram of the copper complex in MeCN at 300 K shows a quasi-reversible peak for the couple CuII/CuIII at Epc = 0.47 and Epa = 0.61 V versus Ag/AgCl and two irreversible peaks for CuII CuI and CuI Cu0 reduction at Epc = –0.63 and – 0.89 V respectively. The e.s.r. spectra of copper and vanadyl complexes in DMSO solution at 300 K and 77 K were recorded and their salient features are reported. The molecular orbital coefficients (2, 2) were calculated for complexes. The antimicrobial activity of the ligand and its complexes have been extensively studied on microorganisms such as Staphylococcus aureus, Klebsiela pneumoniae, Bacillus subtillis, Escherichia coli, Citrobacter ferundii and Salmonella typhi. Most of the complexes have higher activities than that of the free ligand.  相似文献   

12.
Two new vic-dioxime ligands, (E,E)-N-{4-[(1,4-dioxaspiro[4.4]non-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L1H2) and (E,E)-N-{4-[(1,4-dioxaspiro[4.5]dec-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L2H2) containing two different heteroatoms (N,O) have been prepared from anti-chloroglyoxime, N-(1,4-dioxaspiro[4.4]non-2-ylmethyl)butane-1,4-diamine (3) and N-(1,4-dioxaspiro[4.5]dec-2-ylmethyl)butane-1,4-diamine (4). CoII, NiII and CuII complexes of the ligands have a metal:ligand ratio of 1:2 and the ligands coordinate through the two N atoms, as do most of the vic-dioximes. However, ZnII complexes of the ligands have a metal:ligand ratio of 1:1 and the ligands are coordinated only by the N, O atoms of the vic-dioximes. In the CoII complexes two water molecules, and in the ZnII complexes a chloride ion and a water molecule, are also coordinated to the metal ion. The structures of the compounds were determined by a combination of elemental analysis, magnetic moments, molar conductances, thermogravimetric analysis (t.g.a.) and spectroscopic (u.v.–vis., i.r., 1H- and 13C-n.m.r.) data.  相似文献   

13.
Three novel vic-dioximes: cyclohexylamine-p-tolylglyoxime (L1H2), t-butylamine-p-tolylglyoxime (L2H2) and sec-butylamine-p-tolylglyoxime (L3H2) were prepared by the reaction of anti-p-tolylchloroglyoxime with cyclohexylamine, t-butylamine and sec-butylamine in absolute THF. The detection of H-bonding in all of the Ni(II) complexes by i.r. revealed the square-planar MN4 coordination of mononuclear complexes. MN4 coordination of the [(L1H)2Ni] complex was also determined by 1H and 13C-n.m.r spectroscopy. Mononuclear complexes with a 1:2 metal-ligand ratio were prepared using Ni(II) salts. All Ni(II) complexes are insoluble in common solvents. The ligands and complexes were characterized by elemental analyses, FT-i.r., u.v.–vis., 1H and 13C-n.m.r. spectra, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.) and cyclic voltammetry.  相似文献   

14.
Complexes of zinc and iron with N, N2-bis[(1E)-1-(2-pyridyl)ethylidene]ethanedihydrazide (H2L1) and N ,N2-bis[(1E)-1-(2-pyridyl)ethylidene]propanedihydrazide (H2L2) were prepared. ZnII complexes with both ligands have an octahedral geometry. In the complex of ZnII with H2L1, the ligand is coordinated as a tridentate species in the monoanionic form, building two five-membered rings around ZnII. Three remaining coordination sites are occupied by water molecules, and in the outer sphere there is a ClO 4 ion. In the other ZnII complex, the H2L2 ligand is coordinated in the enol form as a tetradenate species, forming a five-memebered, a six-membered and a seven-membered ring, the remaining coordination sites being occupied by water molecules, while in the outer sphere there are two ClO 4 ions. The FeIII complex with H2L2 is a high-spin octahedral complex. The ligand is coordinated in the enol form, in a tetradentate fashion via pyridine and hydrazone nitrogens. The remaining two coordination sites in the complex are occupied by water molecules and a Cl ion, and in the outer sphere there are two Cl anions. The octahedral FeIII complex obtained from the reaction of FeCl3·6H2O and H2L1 in absolute ethanol has the formula [Fe(HL1)Cl2(H2O)]·1.5H2O. However, during coordination of the H2L1 ligand to FeIII in water, oxidative degradation of the side chain (–CO–CO–) and reduction of FeIII to FeII occurs, affording octahedral tris(1-(2-pyridyl)ethylidenehydrazine] ironII perchlorate, as confirmed by X-ray structure analysis.  相似文献   

15.
The novel (E,E)-dioxime,7,8-bis(hydroxyimino)-1,14-bis(monoaza[8]crown-6)-benzo[f]-4,11-dioxa-1,14-diazadecane[7,8-g]quinoxaline (H2L), has been synthesized by the reaction of 6,7-diamino-1,12-bis(monoaza[18]crown-6)benzo[f]-4,9-dioxa-1,12-diazadecane (4) which has been prepared by the reduction of 6,7-dinitro-1,12-bis(mono-aza[18]crown-6)benzo[f]-4,9-dioxa-1,12-diazdecane (3) and cyanogendi-N-oxide. Mononuclear NiII and CuII complexes of H2L have a metal:ligand ratio of 1:2 and the ligand coordinates through two hydroxyimino nitrogen atoms, as do most of the (E,E)-dioximes. The hydrogen-bridged NiII complex was converted into its BF 2 + capped anologue by the reaction with BF3 · Et2O. The reaction of the CuII complex with 2,2′-dipyridyl as an end-cap ligand gave the homotrinuclear complex. Structures for the ligand and its complexes are proposed in accordance with elemental analysis, magnetic susceptibility measurements, 1H, 13C-n.m.r, IR and MS spectral data.  相似文献   

16.
Lin  Hua-Kuan  Wang  Xu  Su  Xun-Cheng  Zhu  Shou-Rong  Chen  Yun-Ti 《Transition Metal Chemistry》2002,27(4):384-389
Three novel compounds, based on the 1,3,5-benzene core with C3-symmetry, have been prepared and characterized by elemental analysis, i.r. and 1H-n.m.r. Thermodynamic properties of the ligands and their CoII, NiII, CuII, and ZnII metal complexes have been investigated and the corresponding stability constants obtained at 25.0 ± 0.1 °C and with I = 0.1 mol dm–3 in KNO3 by potentiometric titration. A linear free energy relationship exists between the stability constants of complexes and the protonation constants of ligands in the ternary system of the CuII-5-substituted phenanthroline-tripod ligand complexes.  相似文献   

17.
Summary New CuII, CoII, NiII, CdII, ZnII, HgII, PdII and UO 2 II complexes of the Schiff base ligand (FBz) formed by condensation of fluorenone withS-benzyldithiocarbazate have been prepared and characterized by elemental analysis, magnetic and spectroscopic measurements. The Cu(FBz)2(Cl)2 complex is paramagnetic. The Ni(FBz-H)2 complex is diamagnetic, four-coordinate and square planar. The CoII ion is oxidized in the presence of the Schiff base with the concomitant formation of CoIII complex of empirical formulae Co(FBz)Cl3OH2. The ligand was tested as a corrosion inhibitor for copper. Inhibition efficiency was calculated and the limiting concentration of FBz to give maximum efficiency was 10–3 mol dm–3 at 25°C. The polarographic reduction of FBz was investigated in Britton-Robinson buffer solutions of pH 3–10. The polarograms at dme indicated that the depolarizer is reduced through two two-electron irreversible diffusion-controlled waves. The mechanistic pathway of the electrode reaction is commensurate with this result.  相似文献   

18.
Summary The kinetics of formation of square-planar CuII and NiII complexes of the quadridentate ligand, ethylenebisbiguanide, have been studied spectrophotometrically in aqueous HOAc–NaOAc buffer, at ionic strength 0.2 mol dm–3, in the 25–35°C temperature range. The observed rate constants for the formation reactions are independent of pH (and of OAc concentration) in the pH range used (3.6–4.8 for CuII and 5.0–5.8 for NiII) where the product complexes form stoichiometrically, but show first-order dependence on the ligand concentration;i.e. kobs=kf[L]total. At 25°C kf values (dm3 mol–1s–1) are 35.2±0.4 for CuII and (8.4±0.1)×10–3 for NiII. The mechanism of the reactions is discussed.  相似文献   

19.
The ligand S-benzyldithiocarbazate (SBDTC) acts as a bidentate sulfur–nitrogen chelating agent. The reaction of SnII or SbIII with SBDTC under alkaline conditions gives complexes of composition [Sn(SBDTCA)2] · 2H2O and [Sb(SBDTCA)Cl2 · 2H2O]. A quadridentate Schiff base of SBDTC with benzil, having a donor sequence SNNS, yields complexes, [Cd(SNNS)] and [Zr(O)(SNNS) · H2O]. The ligands and the complexes have been characterized by elemental analyses, i.r., u.v.–vis., molar conductance measurements and 1H-n.m.r. spectroscopy. SBDTC, SnII and SbIII complexes and the SNNS Schiff base together with its CdII and ZrIV complexes display significant antifungal, antibacterial and anti-cancer activity. The SnII complex and the SNNS free Schiff base were very effective against Melanoma (skin cancer cells). The SBDTC and its SnII complex were also very effective against Renal carcinoma (kidney cancer cells). The results have been compared with those of the uncomplexed metal salts and the free ligands. The minimum concentrations for the evaluation of the above activities for CD50 of the samples were in the 1.0–15 g cm–3 range.  相似文献   

20.
Ge  Qing-Chun  Guo  Yan-He  Lin  Hai  Lin  Hua-Kuan  Zhu  Shou-Rong 《Transition Metal Chemistry》2003,28(5):572-578
The stability constants of ZnII, CuII, NiII and CoII with different tripodal ligands, 1,3,5-tris(2,5-diazaoctxyl)benzene (L1), 1,3,5-tris(2,5-diazanonxyl)benzene (L2) and 1,3,5-tris[3-(2-pyridyl)-2-azapropyl]benzene (L3) have been studied at 25 °C in 0.1 mol dm–3 KNO3 aqueous solution using potentiometric titrations. During the titrations, the ligand concentrations were kept constant at 1 × 10–3 mol dm–3, while 1:1 and 1:3 metal:ligand ratios were used for each system. The results indicated that, in the 1:1 metal:ligand ratio, the binding of MII to the ligand gives rise to several 1:1 complexes differing in their degree of protonation whereas in the 3:1 ratio, polynuclear complexes are formed. Additionally, the ternary complexes of the tripod ligands, with CuII-5-substituted-1, 10-phenanthroline have been investigated and the results show that linear free energy relationship exists in such ternary systems.  相似文献   

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