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1.
Summary Cobalt(II), nickel(II) and copper(II) complexes of 3, 5-dimethyl-1-(4, 6-dimethyl-2-pyrimidyl)pyrazole (DPymPz) have been synthesized and characterized. Magnetic and electronic spectral features show that both [M(DPymPz)2X2nH2O [M=cobalt(II) or nickel(II), X=Cl, Br, I, SCN, NO3, ClO4 or BF4 andn=0 or 2] and [Cu(DPymPz)X2(H2O)2] (X=Cl, Br or SCN) are essentially octahedral species. The i.r. spectra indicate that DPymPz is a neutral bidentate ligand being the pyrazolyl and one pyrimidyl ring nitrogen. The X is bonded to the central metal ion in a majority of the complexes.Part 5: N. Saha and D. Mukherjee,Polyhedron,5, 1317 (1986).  相似文献   

2.
The coordination geometry and supramolecular structures of three copper(II) complexes of two α-hydroxycarboxylates and one α-methoxycarboxylate with nitrogen donor co-ligands are discussed. The complexes have been characterized by elemental analysis, ESI-MS, IR and electronic spectroscopy, thermogravimetric analysis and magnetic measurements. The X-ray structure analysis of all the complexes, namely [(BPCA)CuII(MA)] (1), [(BPCA)CuII(MPA)(H2O)] (2) and [(BPCA)CuII(BA)]n (3), where BPCA = bis(2-pyridylcarbonyl)amidate, MA = racemic mandelate, MPA = racemic α-methoxy phenylacetate and BA = benzilate anion, shows the copper(II) ion in a distorted square-pyramidal geometry. In 1 the mandelate anion is coordinated to the copper(II) center in a bidentate fashion while in 2 the α-methoxycarboxylate is monodentate. In both cases a one-dimensional supramolecular array is formed through hydrogen bonds: the mononuclear units are directly connected in 1 by the MA hydroxyl group, whereas in 2 is the coordinated water that operates as H donor towards the MPA carboxylate group and the BPCA carbonyl oxygens of nearby complexes. In 3 the benzilate anion, acting as bridging ligand between copper ions, gives rise to a one-dimensional coordination polymer. In the latter, intra- and inter-chain π?π stacking interactions between pyridines and one phenyl ring of benzilate anions are observed in the packing.  相似文献   

3.
A new series of hexacoordinate cobalt(II), nickel(II) and copper(II) complexes of 5-(2-carboxyphenylazo)-2-thiohydantoin HL having formulae [LM(OAc)(H2O)2] · nH2O (M = CoII, CuII and NiII), [LMCl(H2O)2] · nH2O (M = CoII and NiII), [LCuCl(H2O)]2 · 2H2O, [LCu(H2O)3](ClO4) and [LCu(HSO4)(H2O)2] were isolated and characterized by elemental analyses, molar conductivities and magnetic susceptibilities, and by i.r., electronic and e.s.r. spectral measurements, as well as by thermal (t.g. and d.t.g.) analyses. The i.r. spectra indicate that the ligand HL behaves as a monobasic tridentate towards the three divalent metal ions via an azo-N, carboxylate-O and thiohydantoin-O atom. The magnetic moments and electronic spectral data suggest an octahedral geometry for CoII complexes, distorted octahedral geometry for both NiII and CuII complexes with a dimeric structure for [LCuCl(H2O)]2 · 2H2O through bridged chloro ligands. The X-band e.s.r. spectra reveal an axial symmetry for the copper(II) complexes with unsymmetrical Ms = ± 1 signal and G-parameter less than four for the dimeric [LCuCl(H2O)]2 · 2H2O. The thermogravimetry (t.g. and d.t.g.) of some complexes were studied; the order and kinetic parameters of their thermal degradation were determined by applying Coats–Redfern method and discussed.  相似文献   

4.
Summary H2O soluble mixed ligand complexes of the type [M-(ADA)B·H2O] where M = NiII or CuII; [ADA]2- = divalent anion of N-(2-acetamido)iminodiacetic acid, B = heterocyclic diimine (2,2'-bipyridyl or 1,10-phenanthroline), were prepared and characterized by elemental and thermal analyses, i.r. and electronic spectra, as well as conductivity measurements. Formation constants for the 111 ternary cobalt(II), nickel(II) and copper(II) complexes formed in solution were determined potentiometrically at 24 °C and = 0.1mol dm-3(KNO3).  相似文献   

5.
The reactions of Cu2+, Co2+, and Ni2+ ions with N-phenyl-N-2-hydroxybenzyl- and N-phenyl-N-2-hydroxynaphthylmethyleneamine derivatives (HL n , n = 1–8) produced from the derivatives of aniline and aromatic -hydroxyaldehydes are studied. Among the ions studied, only Cu2+ forms stable complexes Cu(L n )2 · 2H2O. The structures of the synthesized compounds are studied by IR, UV, and EPR spectroscopies and differential thermal analysis. The magnetic moments of the Cu(L n )2 · 2H2O complexes are very small and range within 0.43–1.19 B, depending on the ligand structure, which indicates a strong antiferromagnetic interaction between the Cu2+ ions. The temperature dependence of the magnetic susceptibility measured for the Cu(L3)2 · 2H2O complex (where HL3 is N-4-methoxyphenyl-N-2-hydroxybenzylamine) is closest to the theoretical curve calculated for the binuclear Cu(II) complexes connected by the intermolecular exchange interaction. The Cu(II) complexes with HL n are shown to undergo oxidative dehydrogenation to form the corresponding metal salicyl-aldiminates. This reaction can occur on heating in the absence of oxygen and is accompanied by the Cu2+ Cu+ transition.  相似文献   

6.
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   

7.
Summary By inhibiting the copper(II) assisted TPT (TPT = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) hydrolysis, monomeric and dimeric copper(II) complexes having as general formulae Cu(TPT)X, · nH2O (X = Cl, Br, NCS, NCO or N3) and [Cu(TPT)X]2(PF6)2 · nH2O (X = Cl, Br, NCS or N3) have been synthesized and characterized by i.r., electronic and e.p.r. spectra, x-ray powder diffraction and analytical data. Spectroscopic results indicate five-coordinate geometry around the copper(II) ion, intermediate between trigonal-bipyramid and square-pyramid structures. The half-field absorption in the MS = 2 region of powdered X-band e.p.r. spectra has been observed for the dimeric species.  相似文献   

8.
Zusammenfassung Die Synthesen und einige Eigenschaften der Verbindungen von zweiwertigem Mn, Cu, Fe, Co, Ni und Zn mit Hydrazidokohlensäure werden beschrieben. Die Verbindungen von Fe, Co, Ni und Zn sind Hydrazinium-hydrazidocarbonato-metallate(II) der allgemeinen Formel N2H5[Me II(N2H3COO)3]·H2O, die von Mn und Cu sind aber einfache Hydrazido-carbonate der FormelMe II(N2H3COO)2·n H2O. Die Ergebnisse magnetochemischer Messungen sowie der orientierender Messungen der thermischen Eigenschaften werden angegeben.
The syntheses and some properties of the compounds of bivalent Mn, Fe, Co, Ni, Cu and Zn with hydrazido-carbonic acid are described. The compounds of Fe, Co, Ni and Zn are hydrazinium hydrazido-carbonato-metallates(II) with the formula N2H5[Me II(N2H3COO)3]·H2O. The compounds of Mn and Cu are hydrazido-carbonatesMe II(N2H3COO)2·n H2O. The results of magnetic and preliminary measurements of thermal properties are given.


J. Slivnik, A. malc, B. Sedej undM. Vilhar, Vestnik SKD (Bull. Soc. chim. Slovène)11, 53 (1964).  相似文献   

9.
Extraction of Hg(II), Se(IV), Mn(II) and Co(II) has been carried out with 1-phenyl-3-methyl-4-trifluoroacetyl-2-pyrazolin-5-one (HPMTFP) and triphenylphosphine oxide (TPPO) into chloroform from pH 1–10. Quantitative extraction of Hg(II), Mn(II) and Co(II) at pH 4 with equimolar 0.05M (PMTFP+TPPO) in chloroform was observed. Se(IV) remains unextracted at this pH range. The stoichiometric composition of the extracted complexes M(PMTFP)2·nH2O (M=Mn, Hg), M(PMTFP)2·2TPPO (M=Mn and Co) and Co(PMTFP)2·TPPO·H2O at less than 0.1M TPPO has been established. The formation constantsK m,0 andK m,n and stability constants m,n have been computed. The analytical method developed was applied to the IAEA standard reference material (SRM) potato fluor V-4 for the determination of these elements using NAA technique.  相似文献   

10.
Benzoylhydrazine, isonitrosoacetone react in ethanol with cobalt, nickel, copper halides andacetates to give the coordination compounds MX2(HL) · nH2O, MX2(HL)2 · nH2O, and ML2 · nH2O [M = Co,Ni, Cu; X = Cl, Br; HL = C6H5C(O)NHNC(CH3)CHNOH; n = 1-4]. The same reactions performed in the presence of sodium acetate and pyridine (pH 7-8) yield the complexes MLCl · nH2O and MPy2LCl ·nH2O (n = 1-4). All the complexes have a pseudooctahedral coordination geometry. The hydrazone HL behaves as a tridentate O,N,N-donor ligand. Thermolysis of the substances involves dehydration (70-90°C), deaquation (155-170°C) or deamination (175-195°C), and complete thermal decomposition (285-360°C).  相似文献   

11.
Zou  Jianzhong  Wu  Yong  Wei  Xianwen  Duan  Chunying  Liu  Yongjiang  Xu  Zheng 《Transition Metal Chemistry》1998,23(4):481-484
Two different products are obtained when 2,3-pyrazinedicarboxylic acid (PzdcH2) reacts separately with two copper(II) salts: Cu(OAc)2 and CuCl2. One product is a mononuclear CuII complex Cu(PzdcH)2·2H2O, the other is a linear polymeric copper(II) complex [Cu(PzdcH)2·2H2O]n, whose structure has been determined by X-ray diffraction at room temperature. The polymeric complex is composed of copper(II) ions, PzdcH- anions and crystal water molecules. The Cu(1) atom is located in elongated octahedral coordination environment with six donor atoms: O(1), N(1), O(1a), N(1a), O(3b) and O(3c) from four different PzdcH- anions. The two oxygen atoms O(3b) and O(3c) come from the carboxylic acid group of the PzdcH- anion of the upper and lower layers, so that an infinite chain constitutes the crystal lattice. There are very strong hydrogen bond interactions between chains which lead to a three-dimensional structure. The magnetic susceptibility of the polymeric complex [Cu(PzdcH)2·2H2O]n has been determined in the 1.5–300K range. A study of magnetic properties shows that a weak antiferromagnetic interaction exists between two copper(II) ions.  相似文献   

12.
An interesting series of nine new copper(II) complexes [Cu2L2(OAc)2]·H2O (1), [CuLNCS]·½H2O (2), [CuLNO3]·½H2O (3), [Cu(HL)Cl2]·H2O (4), [Cu2(HL)2(SO4)2]·4H2O (5), [CuLClO4]·½H2O (6), [CuLBr]·2H2O (7), [CuL2]·H2O (8) and [CuLN3]·CH3OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the dx2-y2 orbital. The structure of the compound, [Cu2L2(OAc)2] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P21/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.  相似文献   

13.
Summary The electrochemical behaviour of a series of monomeric N,N-bis(substituent)oxamidato copper(II) complexes of formula Na2[Cu(3,5,3,5-X4obbz)]·4H2O [X = Cl (1), Br (2), I (3) and obbz = oxamidobis(benzoato)], Na2-[Cu(obbz)]·4H2O (4), Na2[Cu(5,5-Me2obbz)]·4H2O (5), Na2[Cu(4,5,4,5-(MeO)4obbz)]·4H2O(6),Na2[Cu(obp)]· 3.5H2O (7) (obp = oxamidobis(propionato)) and Na2[Cu(pba)]·6H2O (8), [pba = propylenebis(oxamate)] has been investigated by cyclic voltammetry, rotating disk electrode and coulometry in water and dimethylsulphoxide (dmso) solutions. NaNO3 (0.1 M) and n-Bu4NPF6 (0.1 M) were used as supporting electrolytes in H2O and dmso respectively, all solutions being thermostatted at 25 °C. In aqueous solution, the complexes show an oxidation peak ranging from 1.19 to 0.86 V (values referred to the s.c.e.), the corresponding reduction being unobserved, even at high scan rates. In dmso, all the complexes exhibit only one oxidation peak ranging from 0.86 to 0.51 V, the corresponding reduction being observed for all of them except for (3). The oxidation potentials are strongly dependent upon the nature of the N,N-substituent of the oxamide. The copper(III)-assisted hydrolysis of the oxamidate ligand is analysed in terms of the lack of planarity of the oxamidate ligand induced by the steric effect of the halogen substituent in the 3-position on the phenyl rings. The influence of the nature of the solvent was also studied.  相似文献   

14.
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   

15.
In order to deepen our understanding of the versatile behaviour of adenine (Hade) as ligand, we have synthesized four novel ternary copper(II) complexes having two deazaadenine ligands, namely 4-azabenzimidazole (H4abim) or 7-azaindole (H7azain) as N1,N6-dideazaadenine or N1,N6,N7-trideazaadenine, respectively. The related compounds were studied by thermal, spectral and single crystal X-ray diffraction methods. In [Cu(NBzIDA)(H4abim)]n (1) the recognition between H4abim and the (N-benzyliminodiacetate)-copper(II) chelate only displays the formation of the Cu–N7(purine-like) bond, in contrast to Hade behaviour in [Cu(NBzIDA-like)(Hade)(H2O)]·H2O (Cu–N3(Hade) bond reinforced by N9–H···O(IDA-like) interaction). In [Cu(EIDA)(H7azain)(H2O)] (2, EIDA = N-ethyliminodiacetate ligand), [Cu(NBzIDA)(H7azain)(H2O)] (3) and [Cu(μ2-SO4)(H7azain)2(H2O)2]n (4), H7azain binds Cu(II) centre by the Cu–N3(purine-like) bond, reinforced by a N9–H···O(IDA-like or sulfate) intra-molecular interligand interaction.  相似文献   

16.
The synthesis, reduction, optical and e.p.r. spectral properties of a series of new binuclear copper(II) complexes, containing bridging moieties (OH, MeCO2 , NO2 , and N3 ), with new proline-based binuclear pentadentate Mannich base ligands is described. The ligands are: 2,6-bis[(prolin-1-yl)methyl]4-bromophenol [H3L1], 2,6-bis[(prolin-1-yl)methyl]4-t-butylphenol [H3L2] and 2,6-bis[(prolin-1-yl)methyl]4-methoxyphenol [H3L3]. The exogenous bridging complexes thus prepared were hydroxo: [Cu2L1(OH)(H2O)2] · H2O (1a), [Cu2L2(OH)(H2O)2] · H2O (1b), [Cu2L3(OH)(H2O)2] · H2O (1c), acetato [Cu2L1(OAc)] · H2O (2a), [Cu2L2(OAc)] · H2O (2b), [Cu2L3(OAc)] · H2O (2c), nitrito [Cu2L1(NO2)(H2O)2] · H2O (3a), [Cu2L2(NO2)(H2O)2] · H2O (3b), [Cu2L3(NO2)(H2O)2] · H2O (3c) and azido [Cu2L1(N3)(H2O)2] · H2O (4a), [Cu2L2(N3)(H2O)2] · H2O (4b) and [Cu2L3(N3)(H2O)2] · H2O (4c). The complexes were characterized by elemental analysis and by spectroscopy. They exhibit resolved copper hyperfine e.p.r. spectra at room temperature, indicating the presence of weak antiferromagnetic coupling between the copper atoms. The strength of the antiferromagnetic coupling lies in the order: NO2 N3 OH OAc. Cyclic voltammetry revealed the presence of two redox couples CuIICuII CuIICuI CuICuI. The conproportionality constant K con for the mixed valent CuIICuI species for all the complexes have been determined electrochemically.  相似文献   

17.
Summary The new complexes K2[Ni(H2heo)2]·3H2O, K2[Pd-(H2heo)2], K2[Cu(heo)]·3H2O and [Cu2(heo)·2H2O] {heo = [(CONCH2CH2O)2]4-} were prepared and characterized by chemical analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and i.r. and u.v. spectroscopy.Monomeric square planar structures with MN4 coordination spheres are found for the nickel and palladium complex anions.For copper, two different complexes were identified. In slightly alkaline media, a green insoluble nonelectrolyte [Cu2(heo)·2H2O] was prepared; the two copper(II) centres are bridged by the tetra-deprotonated ligand in a trans-planar configuration with the H2O molecules strongly coordinated to the copper(II). The copper(II) monomer has been prepared in strong alkaline media, this anion also contains the tetra-deprotonated ligand in a planar trans form.  相似文献   

18.
Summary Six metal(II) complexes with Morin ML2·nH2O [L = Morin(2-OH group deprotonated); M = Mn, Co, Ni, Cu, Zn, or Cd; n = 2 or 3] have been synthesized and characterized by elemental analysis, molar conductance, i.r., 1H-n.m.r., t.g.-d.t.a and u.v.-vis. spectroscopic techniques and by fluorescence analysis. Comparative antitumour activities of Morin·2H2O and two complexes [ZnL2·3H2O and CuL2·2H2O] were tested by in vitro screening. The results show that the inhibitory ratio of complexes against the tested tumour cells was higher than that of Morin.  相似文献   

19.
Two new copper(II) complexes, [Cu2(bipy)2(H2O)3(tp)(NO3)](NO3) · H2O (1) and [Cu2(bipy)2(tp)2(H2O)] n (2), (tp = terephthalato, bipy = 2,2-bipyridine), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction methods. Complex (1) contains a non-coordinated nitrate anion and an asymmetric binuclear cation in which each copper ion has a distorted square pyramidal coordination geometry with the axial Cu—O distance elongated. The crystal structure of (2) features a zigzag 1D polymeric chain along the diagonal axis of the (0 0 1) plane. Tp adopts two types of coordination mode. In the first mode, both carboxylate groups are unidentate, as in complex (1). In addition to the first mode, the tp ligand in complex (2) also adopts the second coordination mode, in which one carboxylate group is unidentate and the other is bidentately chelating with a copper(II) ion. The magnetic properties of complex (2) have also been studied.  相似文献   

20.
Three new lanthanide(III) complexes of the type [Ln(PBH)2(NO3)(NCS)(H2O)]NO3·nH2O (PBH = 2-pyridinecarboxaldehyde benzoyl-hydrazone) have been prepared from the complexes [Ln(PBH)2(NO3)3]·CH3COCH3·2H2O by anion metathesis reaction and studied by elemental analyses, IR and UV–Vis spectra. The crystal structure of the [Ce(PBH)2(NO3)(NCS)(H2O)]NO32.35H2O complex was determined by X-ray diffraction. The crystals of the compound isothiocyanato-nitrato-aquo-bis[N-(2-pyridinylmethylene)-N-benzoyl-hydrazino]-cerium(III) nitrate 2.35 hydrate are monoclinic with crystallographic P21 n symmetry. The coordination sphere consists of two tridentate 2-pyridinecarboxaldehyde benzoylhydrazone, one bidentate nitrate, one isothiocyanate, and one water molecule as ligands. The coordination polyhedron around the cerium atom can be described as a distorted bicapped square antiprism. The coordination of the hydrazone ligand to the metal atom is accomplished through the pyridine nitrogen, the azomethine nitrogen, and the carbonyl oxygen.  相似文献   

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