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1.
Summary N-benzamidosalicylaldimine (H2L) complexes of CuII, NiII, CoII, FeII, MnII. VOIV and TiOIV have been prepared. The ligand probably coordinates to the metal from the hydroxyl, carbonyl and imino groups.  相似文献   

2.
Summary 2-Aminoacetophenone-2-thenoylhydrazone, Haath, C4H3SC(O)NHN=C(Me)C6H4NH2-o, forms complexes with metal(II) salts of empirical compositions [VO(Haath)2SO4], [M(Haath)2Cl2] [M=CoII, NiII, CuII or ZnII] and [M(aath)2] [M=VIVO, CoII, NiII, CuII or ZnII] which have been characterized by elemental analyses, molar conductance, magnetic susceptibility, electronic, e.s.r., i.r. and n.m.r. (1H and13C) spectral studies. X-ray and electron diffraction patterns have been obtained in order to elucidate the structure of the CuII complexes. Photoacoustic spectra of powder NiII complexes have been recorded and interpreted in the light of u.v./vis. spectra.  相似文献   

3.
A series of asymmetric heterobimetallic complexes of the type [LMLSn]Cl and [LMLSn]Cl2, where L = ethylene diamine, M = MnII, CoII, NiII and CuII, M = CrIII and FeIII and L = 1-tryptophan and 1-valine, have been synthesized and characterized by elemental analyses, u.v.–vis., i.r., e.p.r., n.m.r., cyclic voltammetry and conductivity measurements. The CoIII analogue of these complexes was characterized by two dimensional n.m.r. COSY data. The kinetics of oxygen binding with the complex [C15H23N4O2SnCo]Cl has also been studied. The kinetic data proves that CoII of a coordinated molecule participates in the rate-determining step of the dioxygen binding process. The plots of the pseudo-first-order rate k obs versus [O2] are linear passing through an intercept. The electrochemical behaviour of [C15H23N4O2SnCo]2+ and [C15H23N4O2SnCu]+ was monitored by cyclic voltammetry. Comparison of the electrochemical properties of [CoIIISnIV]2+ and [CuIISnIV]+ reveal that, in both the species, one electron transfer reaction takes place. For the [CoIIISnIV]2+ species E 0 = 0.272 and –1.1 V and for the [CuIISnIV]+ species E 0 = 0.078 and –0.300 V values were obtained, respectively.  相似文献   

4.
Transition metal (NiII, CoII, and CuII) complexes with 1,2-bis[2-(3-pyridylmethylideneamino)phenylthio]ethane (1) and 1,2-bis[2-(4-pyridylmethylideneamino)phenylthio]ethane (2) were synthesized for the first time by slow diffusion of solutions of compounds 1 or 2 in CH2Cl2 into solutions of MX2 · nH2O (M = Ni, Co, or Cu; X = Cl or NO3; n = 2 or 6) in ethanol. The reactions with CoII and CuII chlorides afford complexes of composition M(L)Cl2 (L = 1 or 2). The reactions of compound 1 with NiII salts produce complexes with 1,2-bis(2-aminophenylthio)ethane. The molecular structure of dinitrato[1,2-bis(2-aminophenylthio)ethane]nickel(ii) was confirmed by X-ray diffraction. The ligands and the complexes were investigated by cyclic voltammetry and rotating disk electrode voltammetry. The initial reduction of the complexes proceeds at the metal atom. The oxidation of the chlorine-containing complexes proceeds at the coordinated chloride anion. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–355, February, 2008.  相似文献   

5.
We describe the synthesis, characterization and electrochemistry of a new family of peripherally functionalised vic-dioxime, 5,6-bis-(hydroxyimino)-1,2,9,10-hydroxy-4,7-dithiadecane (LH2), with bis-(thiopropandiol) moieties attached to the oxime. Thiopolyalcohol groups containing two different heteroatoms (—S— and —O—) serve as weak exocyclic binding sites for Pd+2 and Ag+ ions. Novel mononuclear (LH)2M, (M = NiII, CuII, CoII, MnII and FeII), homodinuclear (LH)2(UO2)2(OH) and heterotrinuclear (LH)2MM2 (M = NiII and M = PdII and AgI) species have been obtained with the metal:ligand ratios of 1:2, 2:2, and 3:2 respectively. Metal ions coordinate through N,N of the oxime and S,O donor sites of the peripherally attached groups in the presence of the base. The heterotrinuclear complexes were prepared by the interaction of the mononuclear complex, (LH)2Ni, with Pd(C5H5)2 and AgNO3 in an appropriate solvent. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.–vis. spectroscopy, FT-IR., and by f.a.b-m.s. The redox properties of the complexes were studied by cyclic voltammetry.  相似文献   

6.
Reactions of hydroxyethyl cellulose (HEC) with Cr III, NiII, CoII, or CuII chlorides in aqueous medium yielded complexes with formulae [M(HEC)Cl m .n H 2O], wherem =1 or 2 and n=2 or 3. HEC acted as a uninegatively charged bidentate ligand in the case of CrIII and NiII, and as a neutral ligand in the case of CoII and CuII complexes. The spectra showed that the binding sites in CrIII and NiII complexes were the ether oxygen between two ethoxyl groups and the oxygen of the hydroxyl group; while in the CoII and CuII complexes the binding sites were the oxygen of ethoxyl groups and the primary alcoholic O atom of glucopyranose rings. These complexes would most likely exhibit octahedral geometry with CrIII, NiII, and CoII, but square planar configuration in the case of the CuII complex. The ligand parameters of the CrIII, NiII, and CoII metal chelates were calculated in different solvents and at different temperatures. The thermal stability of the above complexes was investigated and the overall thermodynamics functions G0, H0, and S0, associated with complex formation, were estimated.  相似文献   

7.
CoII,III, NiII, and CuII complexes of new dehydroacetic acid N4-substituted thiosemicarbazones have been studied. The substituted thiosemicarbazones, N4-dimethyl-(DA4DM), N4-diethyl-(DA4DE), 3-piperidyl-(DApip) and 3-hexamethyleneiminyl-(DAhexim), when reacted with the metal chlorides, produced two CoII complexes, [Co(DA4DE)Cl2] and [Co(DAhexim)2Cl2]; two CoIII complexes, [Co(DA4DM-H)2Cl] and [Co(DApip-H)(DApip-2H)]; a paramagnetic NiII complex, [Ni(DAhexim)(DAhexim-H)Cl]; three diamagnetic NiII complexes, [Ni(DA4DM-H)Cl], [Ni(DA4DE-H)Cl] and [Ni(DApip-H)Cl]; and four CuII complexes with the analogous stoichiometry of the latter three NiII complexes. These new thiosemicarbazones have been characterized by their melting points, as well as i.r., electronic and 1H-n.m.r. spectra. The metal complexes have been characterized by i.r. and electronic spectra, and when possible, n.m.r. and e.s.r. spectra, as well as elemental analyses, molar conductivities, and magnetic susceptibilities. The crystal and molecular structure of the four-coordinate CuII complex, [Cu(DAhexim-H)Cl] has been determined by single crystal X-ray diffraction and the anionic ligand coordinates via an oxygen of the dehydroacetic acid and the thiosemicarbazone moiety's imine nitrogen and thione sulfur.  相似文献   

8.
The study reports the synthesis of complexes Co(HL)Cl2 ( 1 ), Ni(HL)Cl2 ( 2 ), Cu(HL)Cl2 ( 3 ), and Zn(HL)3Cl2 ( 4 ) with the title ligand, 5‐(pyrazin‐2‐yl)‐1,2,4‐triazole‐5‐thione (HL), and their characterization by elemental analyses, ESI‐MS (m/z), FT‐IR and UV/Vis spectroscopy, as well as EPR in the case of the CuII complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the ZnII ion in 4 is coordinated by the non‐protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine CoII, NiII, and ZnII complexes in 10/90 (v/v) DMSO/water solution, whereas the CuII complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L:M = 1:1 species with CoII, NiII and ZnII, the 2:1 species with CoII and ZnII, and the 3:1 species with ZnII. A distorted tetrahedral arrangement of the CuII complex was suggested on the basis of EPR and Vis/NIR spectra.  相似文献   

9.
A new alcohol soluble functionalized vic-dioxime, bis-[(1-hydroxyhexyl)-(8,9-hydroxyimino)-7,10-dithiahexacosane (LH2), and its alcohol-soluble mono and dinuclear complexes (NiII, CuII, CoII, MnII, PdII and UO 2 II ) have been prepared from 6-mercapto-1-hexanol and (E,E)-dichloroglyoxime under high dilution basic conditions. Reactive polyalcohol moieties appended at the periphery of the oxime containing two different heteroatoms (S-, O-), serve as a weak exocyclic binding sites for PdII and AgI metal ions and also provide solubility for the vic-dioxime complexes in low molecular-weight alcohols. Both mono-nuclear (LH)2M and homodinuclear (LH)2(UO2)2(OH)2 and heterotrinuclear (LH)2MM 2 Xn, where M = CoII M′ = PdII, X = Cl, n = 4 and AgI X = NO 3 , n = 2) complexes have been obtained with a 1:2, 2:2, 3:2 metal/ligand ratio, respectively. Electronic spectra of the modified vic-dioximes exhibit monitorable changes in UV. All mono and dinuclear-complexes are soluble in common organic solvents. The elemental analysis, 1H-n.m.r, i.r., u.v–vis, and f.a.b.–m.s data and by cyclic and differential pulse voltammetry measurements are presented.  相似文献   

10.
Summary Complexes having the chemical compositions [VO(Habth)2SO4], [M(Habth)2Cl2] [M=CoII, NiII, CuII or ZnII) and [M(abth)2] [M=VIVO, CoII, NiII, CuII or ZnII) and Habth=2-aminobenzophenone-2-thenoylhydrazone] have been prepared and characterized. The complexes are non-electrolytes. Magnetic moments and electronic, photoacoustic, e.s.r. and i.r. spectra of the complexes are used to establish the stereochemistry and mode of bonding of the hydrazone.  相似文献   

11.
Radical anion salts of metal‐containing and metal‐free phthalocyanines [MPc(3?)].?, where M=CuII, NiII, H2, SnII, PbII, TiIVO, and VIVO ( 1 – 10 ) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C?Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1 – 10 show new bands at 833–1041 nm in the NIR range, whereas the Q‐ and Soret bands are blue‐shifted by 0.13–0.25 eV (38‐92 nm) and 0.04–0.07 eV (4–13 nm), respectively. Radical anions with NiII, SnII, PbII, and TiIVO have S=1/2 spin state, whereas [CuIIPc(3?)].? and [VIVOPc(3?)].? containing paramagnetic CuII and VIVO have two S=1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal‐free phthalocyanine radical anions [H2Pc(3?)].? (linewidth of 0.08–0.24 mT), broad EPR signals are manifested (linewidth of 2–70 mT) with g‐factors and linewidths that are strongly temperature‐dependent. Salt 11 containing the [NaIPc(2?)]? anions as well as previously studied [FeIPc(2?)]? and [CoIPc(2?)]? anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3?)].? in 1 – 10 .  相似文献   

12.
CoII, NiII, CuII, ZnII and CdII complexes of N,N-bis(2-{[(2-methyl-2-phenyl-1,3-dioxolan-4-yl)methyl]amino}butyl)N′,N′-dihydroxyethanediimidamide (LH2) were synthesized and characterized by elemental analyses, IR, 1H- and 13C-NMR spectra, electronic spectra, magnetic susceptibility measurements, conductivity measurements and thermogravimetric analyses (TGA). The CoII, NiII and CuII complexes of LH2 were synthesized with 1?:?2 metal ligand stoichiometry. ZnII and CdII complexes with LH2 have a metal ligand ratio of 1?:?1. The reaction of LH2 with CoII, NiII, CuII, ZnII and CdII chloride give complexes Ni(LH)2, Cu(LH)2, Zn(LH2)(Cl)2, Cd(LH2)(Cl)2, respectively.  相似文献   

13.
The binaphthyl macrocyclic ligand, N,N′-diethyl-[3,3′-(2,2′-dihydroxy-1,1′-binaphthyl)carboxamide]-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid (DDCDB), has been synthesized and investigated. The ligand (DDCDB) and its metal complexes involving CuII, ZnII, UO 2 II , ThIV, CeIII, MoVI and WVI ions have been prepared and characterized by spectral (i.r., u.v.–vis.), elemental analyses, magnetic moments and thermal analyses measurements. DDCDB behaves as a tridentate ligand towards CuII, ZnII and UO 2 II ions coordinating via CO, NH and the deprotonated naphthyl OH groups in a ratio of 2:1 (M:L). On the other hand, DDCDB behaves in a bidentate manner coordinatingvia the NH and the deprotonated naphthyl OH groups only in case of the ThIV, CeIII, MoVI, and WIV ions and in ratio 1:1 (M:L). Results of thermal measurements confirm the existence of solvent molecules inside and outside the coordination sphere. ThVI complex has been applied for the hydrolysis of phosphodiester and the results show a significant rate enhancement of ~5.8 million fold with respect to the auto-hydrolysis of bis-(p-nitrophenyl) phosphate (BNPP) under the same conditions Also, CuII complex accelerates the photodegradation of the hazardous pollutant (acid green dye) in the presence of hydrogen peroxide by degrading 90% of the dye within 23 min.  相似文献   

14.
Condensation of 1H-pyrazole-3,5-dicarboxylic hydrazide with 1H-indole-2,3-dione (isatin) yield the compartmental ligand, which is capable of encapsulating two transition metal ions namely CoII, NiII, CuII, and ZnII. The ligand is a binuclear hexadentate chelate with N4O2 donating sites. The pyrazole core provides the diazine fragment, which serves as an endogenous bridge between the two metal centers. In CoII and NiII complexes, the ligand is in the imidol form and the subsequent coordination through the imidol oxygen. In other complexes, the lactonic oxygen takes part in ligation. All the complexes are non-electrolytes and soluble in DMSO, DMF, and acetonitrile. Spectral and magnetic studies along with analytical data suggest octahedral geometry for the CoII and NiII complexes, whereas the CuII and ZnII complexes are assigned square pyramidal geometry. The CuII and NiII complexes show one electron redox behavior and the rest are electrochemically inactive.  相似文献   

15.
Summary A number of metal complexes of the ligand tetramethylethylenediaminetetraacetate [Edta(OMe)4 = L] have been characterised. The complexes may be formulated MLCl2 · xH2O where M2+ = MnII, FeII, CoII, NiII, CuII, CdII, HgII and SnII. I.r., conductivity, magnetic susceptibility and electronic spectral data are discussed.  相似文献   

16.
The reaction of 3-formylsalicylic acid with 1,2-bis(o-aminophenylthio)ethane yielded a Schiff base with eight donor centres N2S2O4 of which the inner compartment is of an N2S2O2 type and the outer is of the O2O2 type. The base forms several mononuclear homo- and hetero-dinuclear complexes: e.g. mononuclear CuII, NiII and dinuclear CuII, NiII, UO2 VI complexes. Hetero-dinuclear complexes {[M]M}, where M = the inner metal ion CuII, NiII and M = the outer metal ion PdII, UO2 VI are also reported. The complexes were characterised by elemental analyses, spectral, thermal and magnetic measurements. Dicopper and dinickel complexes exhibit subnormal magnetic moments showing spin pairing between two metal centres, via the phenolato oxygen, whereas other mono-copper and mono-nickel complexes (both mononuclear and hetero-dinuclear) show the expected magnetic behaviour for 1e and 2e, respectively. The e.s.r. spectra of copper complexes also support the above behaviour.  相似文献   

17.
In this study, the Schiff base ligands H2L1–H2L3 and their CuII, CoII, NiII, FeIII RuIII and VOIV complexes have been prepared and characterized by spectroscopic and analytical techniques. All the complexes are mononuclear. Keto-enol tautomeric forms of the ligands have been investigated in polar and apolar solvents. The ligands favor the keto-form in the C7H8 and C6H14. The C–C coupling reaction of the 2,6-di-t-butylphenol has been investigated by the CoII and CuII complexes. Thermal properties of the complexes have been assessed using thermal techniques and similar properties were found. In the FeIII and RuIII complexes, firstly, the coordinated water molecule is lost from the complex; in the second step, the chloride ion leaves the molecule in the 300–350 °C temperature range. Finally, the complexes decompose to the appropriate metal oxide at the higher temperature ranges. The electrochemical properties of the complexes have been studied in the two different solvents (DMF and CH3CN).  相似文献   

18.
Several new complexes of a tridentate ONS Schiff base derived from the condensation of S-benzyldithiocarbazate with salicylaldehyde have been characterised by elemental analyses, molar conductivity measurements and by i.r. and electronic spectra. The Schiff base (HONSH) behaves as a dinegatively charged ligand coordinating through the thiolo sulphur, the azomethine nitrogen and the hydroxyl oxygen. It forms mono-ligand complexes: [M(ONS)X], [M=NiII, CuII, CrIII, SbIII, ZnII, ZrIV or UVI with X = H2O, Cl]. The ligand produced a bis-chelated complex of composition [Th(ONS)2] with ThIV. Square-planar structures are proposed for the NiII and CuII complexes. Antimicrobial tests indicate that the Schiff base and five of the metal complexes of CuII, NiII, UVI, ZnII and SbIII are strongly active against bacteria. NiII and SbIII complexes were the most effective against Pseudomonas aeruginosa (gram negative), while the CuII complex proved to be best against Bacillus cereus (gram positive bacteria). Antifungal activities were also noted with the Schiff base and the UVI complex. These compounds showed positive results against Candida albicans fungi, however, none of them were effective against Aspergillus ochraceous fungi. The Schiff base and its zinc and antimony complexes are strongly active against leukemic cells (CD50 = 2.3–4.3 μg cm−3) while the copper, uranium and thorium complexes are moderately active (CD50 = 6.9–9.5 μg cm−3). The nickel, zirconium and chromium complexes were found to be inactive. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

19.
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   

20.
A new vic-dioxime bearing coumarin functionality, N1,N2-Dihydroxy-N 1,N 2-bis(4-methyl-2-oxo-2H-chromen-7-yl)oxalimidamid (LH2), N,N-bis-[4-methylcoumarinyl]-diamino glyoxime (LH2), and its mono- and dinuclear complexes {copperII, cobaltII, nickelII and uranylII} have been reported. The fluorescence excitation and emission spectra of LH2 and its complexes with metal ions were examined. It was observed that fluorescence and excitation emission intensity of LH2 was quenched depending on complex formation with metal ions. The characterizations of all newly synthesized compounds were made by elemental analysis, 1H-n.m.r, i.r., u.v.–vis., and l.c-m.s./m.s. data. Electrochemical behaviour of the ligand involving oxime and coumarine moieties, and its complexes with NiII, CuII, CoII and UO 2 II were investigated by cyclic voltammetry. The comparison of the electrochemical behaviour of the ligand with its complexes enabled us to identify metal-, oxime- and coumarine-based signals.  相似文献   

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