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1.
Two copper(II) complexes with the general formula [Cu(L)(H2O)](ClO4)2 (1) and [Cu(L)2](ClO4)2 (2), where L=3-((pyridin-2-ylmethyl)amino)propanamide, were synthesized and characterized by elemental analyses, IR, UV–vis spectroscopy techniques and molar conductance measurements. The crystal structures of the complexes were identified by single crystal X-ray diffraction analysis. The tridentate ligand L acts as an N2O-donor through the nitrogen atoms of the pyridine and amine moieties as well the oxygen atom of the amide group. The copper(II) ions in both complexes have distorted octahedron structures so that the Cu(II) ion in 1 is coordinated by an aqua ligand and a tridentate ligand defining the basal plane, and by two oxygen atoms of the perchlorate ions occupying the axial positions. However, two ligands L are coordinated to the copper(II) ion in 2, where four nitrogen atoms of pyridine and amine groups occupy the equatorial positions and two oxygen atoms of the amide moieties exist in the apices. The chromotropism (halo-, solvato- and ionochromism) of both complexes were studied using visible absorption spectroscopy. The complexes are soluble in water and organic solvents and display reversible halochromism. The solvatochromism property is due to structural change followed by solvation of the vacant sites of the complexes. The complexes demonstrated obvious ionochromism and are highly sensitive and selective towards CN? and N3? anions in the presence of other halide and pseudo-halide ions.  相似文献   

2.
A new vic-dioxime ligand, N,N′-bis(aminopyreneglyoxime) (LH2), and its copper(II), nickel(II) and cobalt(II) metal complexes were synthesized and characterized by elemental analyses, IR, UVVIS and 1H and 13C NMR spectra (for the ligand). Mononuclear complexes were synthesized by a reaction of ligand (LH2) and salts of Co(II), Ni(II), and Cu(II) in ethanol. The complexes have the metal-ligand ratio of 1: 2 and metals are coordinated by N,N′ atoms of vicinal dioximes. The ligand acts in a polydentate fashion bending through nitrogen atoms in the presence of a base, as do most vic-dioximes. Detection of a H-bonding in the Co(II), Ni(II), and Cu(II) complexes by IR revealed the square-planar MN4 coordination of mononuclear complexes. Fluorescent properties of the ligand and its complexes arise from pyrene units conjugated with a vic-dioxime moiety. Fluorescence emission spectra of the ligand showed a drastic decrease in its fluorescence intensity upon metal binding. The electrochemical properties of the complexes were studied by the cyclic voltammetry technique. The nickel complex displayed an irreversible oxidation process while the copper complex exhibited a quasi-reversible oxidation and reduction processes based on the copper Cu(II)/Cu(III) and Cu(II)/Cu(I) couples, respectively.  相似文献   

3.
Silver(I) and copper(I) complexes of C2-symmetric bis(oxazoline) ligands were studied by UV, NMR, IR, EPR and ES-MS spectroscopies. The stability constants of the Ag-1a and Ag-1b complexes with 1:1 and 1:2 stoichiometries in acetonitrile were determined by NMR spectrometric titrations. The evidence of tetrahedral coordination for complex (Ag(1a)2(+ was obtained from the complexation induced shifts (CIS) and NOEs. Mass spectra revealed the Cu(II) mediated oxidation of methylene bridge in copper complexes of 1a and 1b, which was in accordance with the UV, NMR, IR and EPR findings. The efficiency of Cu(I) complexes of methylene-bridged 1,5-bis(oxazoline)s 1 as chiral catalysts in stereoselective cyclopropanation of styrene with ethyl diazoacetate, was compared to that of the dialkylmethylene-bridged 1,5-bis(oxazoline)s 2.  相似文献   

4.
《印度化学会志》2022,99(3):100363
Two new Cu(II)–Zn(II) complexes as a discrete hexanuclear cluster [{(CuL1)2Zn}21,5-N(CN)2)2](ClO4)2 (1) and a two dimensional (2D) coordination polymer [(CuL2)2Zn(μ1,5-N(CN)2)2]n (2) have been isolated by mixing two similar tetradentate Schiff bases H2L1 (N,N′-bis(ɑ-ethylsalicylidene)-1,3-propanediamine) and H2L2 (N,N′-bis(salicylidene)-1,3-pentanediamine) separately with Cu(ClO4)2·6H2O, Zn(ClO4)2·6H2O and NaN(CN)2 ?at same reaction condition. The heterometallic complexes have been structurally characterized by single crystal X-ray analyses showing that both are formed by angular trinuclear nodes and μ1,5-dicyanamide spacers. The trinuclear nodes ([(CuL1)2Zn]2+ in 1 and [(CuL2)2Zn]2+ in 2 are produced in situ from their corresponding reactants. The two Schiff base ligands coordinating the Cu(II) ions through the N2O2 donor set are additionally bonded to a Zn(II) ion with the four phenoxido oxygen atoms that act as bridging atoms. The zinc ion completes its coordination geometry with two terminal nitrogen atoms of two different dicyanamide spacers. The orientation of spacers from zinc ion are convergent in 1 whereas divergent in 2. Thus, two [(CuL1)2Zn]2+ nodes are interconnected by double μ1,5-dicyanamide bridges via Zn(II) centres to form discrete hexanuclear assembly of complex 1. On the other hand, [(CuL2)2Zn]2+ nodes in 2 are joined by μl,5-dicyanamide that bridge Zn(II) to Cu(II) centres of symmetry related units in order to construct a 2D coordination polymer. Consequently, the final coordination environment around Zn(II) is octahedral in both complexes whereas that around Cu(II) are square planar and square pyramidal in 1 and 2 respectively.  相似文献   

5.

The title complex [K{Cu(acen)}3]2[Co(NCS)4]·1/4CH3OH (acen = acetylacetonethylenediamine anion) has been prepared and characterized. Single-crystal x-ray analysis reveals that the complex crystallizes in space group P I with a = 11.442(2), b = 15.098(3), c = 28.500(4) Å, α = 82.77(1), β = 83.58(1), γ = 85.07(1)°. The crystal consists of the complex [K{Cu(acen)}3]+ cations, [Co(NCS)4]2? anions and methanol molecules. Three [Cu(acen)] molecules function as bridging ligands through phenolic O atoms to one K+ to give the tetranuclear [K{Cu(acen)}3]+ cation. Each copper(II) atom in the cation is in a square-planar geometry, being coordinated by two oxygen atoms and two nitrogen atoms from a quadridentate acen ligand. The cobalt(II) atom is coordinated by four nitrogen atoms of thiocyanate ligands, forming a deformed tetrahedral environment. The IR and UV-Vis spectra have also been investigated.  相似文献   

6.
At room temperature, the chain-like polymeric copper (II) complexes bridged by bis (diphenylphosphino oxide) ethane (dppeO2), [Cu(dppeO2)X2]n[X=Cl(1), Br(2)] have been prepared and characterized by elemental analysis, 31P NMR, TG-DTA and X-ray analysis for [ CuBr2 (dppeO2) ] n The chain is composed of subunits containing tetrahedron coordinated copper (II) atoms. The four-coordinated copper (II) atom is ligated to another four-coordinated copper (II) atom through dppeO2. The coordination sphere of copper(II) atom is completed by two monodentate bromide and two oxygen atoms from bridging dppeO2. Crystal data are as follows: C26-H24CuP2BnO2, 0.50 mm× 0.40 mm×0.40 mm, monoclin-ic, space group: C2/c, λ= 0.07107 nm(Mo Ka), a = 1.2286(2) nm, b=2.0555(8) nm, c = 1.0652(2) nm, β = 97.366(9)°, V = 2.668nm3, Z = 4, Dcalc = 1.628 g·cm-3, R = 0.066; Rw = 0.091.  相似文献   

7.
Cu(II) and Zn(II) complexes were synthesized from equimolar amounts of carboxamides; 1,8-bis(2-thiophenecarboxamido)-p-menthane (tkdam) and 1,8-bis(2-furancarboxamido)-p-menthane (furdam). The structure of the carboxamides were determined by elemental analysis; 1H NMR, 13C NMR, FT-IR and LC-MS spectra. The relative energies and the electronic properties (LUMO, HOMO, LUMO-HOMO gap) of the ligands were investigated theoretically by performing Semi-empirical molecular orbital theory PM3 method in Hyperchem 7 (Release). Carboxamide complexes having general formula as; monomeric, [ML]Cl2 and dimeric [Cu(tkdam)Cl]2Cl2 · 5H2O were synthesized and characterized by using element analysis; FT-IR, LC-MS spectra; magnetic susceptibility, molar conductivity and thermal (TGA/DTA curve) studies. It was found that the coordination number of the monomeric complexes is four whereas dimeric’s is six. The changes in the selected vibration bands in FT-IR indicate that, carboxamides behave as tetradentate ligands and coordinate to metal ions from acyl ring (through S/O) and amide carbonyl (C=O). Molar conductivity measurements indicate the 1: 2 ionic nature of the carboxamide complexes.  相似文献   

8.
Abstract

The compounds [Cu(oxpn)] (1), [(bpy)(H2O)Cu(μ-cis-oxpn)Cu(H2O)] · 2NO3 · 2H2O (2) and [(Him)(NO3)Cu(μ-trans-oxpn)Cu(Him)(NO3)] (3), where oxpn is the dianion of N,N′-bis(3-aminopropyl)oxamide, bpy is bipyridine and Him is imidazole, were prepared and characterized by elemental analysis and IR spectra. Complex (2) was also studied by thermochemical analysis and its structure determined by X-ray crystallography. The structure of complex (2) consists of binuclear copper(II) molecules in which the copper(II) atoms are bridged by an oxamidato group in the cis conformation resulting a copper-copper distance of 5.21 Å. Both copper(II) ions are in square-pyramidal surroundings with almost coplanar basal planes and a water molecule occupying the apical positions. The N atoms of the oxamidato moiety are trigonal. Two lattice water molecules together with the two coordinated ones hydrogen bond with nitrate ions.  相似文献   

9.
The nickel(II) and copper(II) complexes of meso-3,6,6,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime (meso-HM-PAO) have an intramolecular hydrogen bond between cis oxime groups. [Cu(meso-HM-PAO-H)(H2O)](NCS) crystallizes in space group P21/n with a = 7.692(1), b = 12.028(2), c=20.235(3) Å, β=93.03(1)°, Z = 4 and Dc=1.46 g/cm3. The final R value for this complex was 0.034 for 2223 observed reflections with I ≥ 2.5σ (I). The Cu(II) coordination is a distorted square pyramid. The Cu(II) ion is five-coorinated with the diazadioxime N atoms equatorial and water O atom axial. The Cu(II) is 0.12 Å from the equatorial plane towards the hydrate. The equatorial Cu-N distances span a narrow range, 1.953(3)-1.999(3) Å. The axial Cu-O distance is 2.314(3) Å. The thiocyanate group is almost linear. The intramolecular O ?O hydrogen bond length is 2.479(4) Å. [Ni(meso-HM-PAO-H)](ClO4) crystallizes in space group P21/c with a = 14.774(3), b = 12.752(3), c = 20.035(4) Å, β = 92.94(3)°, Z = 8 and Dc = 1.51 g/cm3. The final R value for the complex was 0.053 for 4794 observed reflections with F ≥ 4σ (F). The coordination about Ni(II) is a slightly distorted square plane. The Ni(II) ion is 0.0673(7) Å from the best plane of the four donor nitrogen atoms away from the perchlorate ion. The Ni-N distances span a narrow range 1.863(4)-1.927(4) Å. There are two molecules per asymmetrical unit resulting in eight molecules being packed in an unit cell; they are bound together by van der Waals interactions. The O-H ?O bonds of these complexes give characteristic infrared absorptions as well as chemical shift of the 1H NMR signal (Ni complex).  相似文献   

10.
Abstract

A novel dioxime, 1,2 dihydroxyimino-3,7-diaza-9,10-O-benzaloctane (LH2) was prepared by reaction of l,2-0-benzylidene-4-aza-7-aminoheptane and anti-phenylchloroglyoxime in absolute ethanol. Mononuclear complexes with a metal-ligand ratio of 1:2 were prepared with Co(II), Cu(II) and Ni(II). To elucidate the structures of the ligand and complexes, elemental analyses, IR, 1H NMR and 13C NMR spectral data and magnetic susceptibility measurements have been examined.  相似文献   

11.
Abstract

The coordination properties of 5-amino-1,3,4-thiadiazole-2-sulfonamide (Hats) with Cu(II), Ni(II) and Zn(II) ions, are analyzed. Although the ligand presents several donor atoms, we have only observed three coordination behaviors: (i) as a monodentate ligand through the Nsulfonamido atom, (ii) as a bridging ligand linking the metal ions through the Nsulfonamido and Nthiadizole atoms and (iii) as a bridging ligand linking metal ions through the N and O atoms of the sulfonamidate group. It is noteworthy that coordination mode (iii) is observed for the first time in heterocyclic sulfonamides complexes. In addition, the conformation of the Hats as counter-ion is analyzed and compared with the conformations that the ligand adopts in metal complexes.  相似文献   

12.
Ruthenium(II) and palladium(II) complexes [Ru(DMSO)(L)Cl2] and [Pd(L)Cl]Cl, where L = 2,6-bis(pyrazol-1-yl)pyridine (bpp) or 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine (bdmpp) have been synthesized. All complexes were characterized by elemental analysis, IR, 1H NMR, UV-Vis, and cyclic voltammetry measurements.  相似文献   

13.
The new Co(II), Cu(II), Ni(II) and Zn(II) complexes of potentially N2O2 Schiff base ligand [N,N’-bis(salicyldehydene)-1,4-bis-(o-aminophenoxy)butane] (H2L) prepared from 1,4-bis-(o-aminophenoxy)butane and salicyldehyde in DMF. Microanalytical data, elemental analysis, magnetic measurements, lH NMR, 13C NMR, UV-visible and IR spectra as well as conductance measurements were used to confirm the structures. In all complexes, H2L behaves as a tetradentate. The article is published in the original.  相似文献   

14.
A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H2Pymdo) (3) has been synthesized in H2O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H2Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H2Pymdo) and its copper(II) complexes were characterized by 1H-n.m.r., 13C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H2Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H2Pymdo and its Cu(II) complexes.  相似文献   

15.
[Cu(L)(NO3)2] (1) and [Cu(L)(H2O)2](SCN)2 (2) [L?=?3,14-diethyl-2,6,13,17-tetraazatricyclo(16.4.0.07,12)docosane] have been prepared and structurally characterized by single-crystal X-ray diffraction at 100?K. For these constrained macrocycle complexes, copper(II) exists in a tetragonally distorted octahedral environment with the four nitrogen atoms of the macrocyclic ligands and two oxygen atoms from either nitrate or water in axial positions. The macrocyclic ligands in both complexes adopt the most stable trans-III conformation. The Cu–N distances are 2.021(2)–2.047(2)?Å and typical but the axial ligands are weakly coordinating, with Cu–O bond lengths, 2.506(2)?Å for 1 and 2.569(2)?Å for 2, due to the pseudo Jahn–Teller effect. The crystals are stabilized by a 3-D network by intra and intermolecular hydrogen bonds that are formed among the secondary nitrogen hydrogen atoms and nitrate in 1, and intermolecular hydrogen bonds are formed by water and thiocyanates in 2. The electronic absorption and IR spectral properties are also discussed.  相似文献   

16.
The new cyclodiphosph(V)azane derivatives (1,3-dimethyl-2,4-dioxo-2',4'-bis(2,4-bis(dimethylaminopropylimino)cyclodiphosph(V)azane (H2L1) (1,3-dimethyl-2,4-dioxo-2',4'-bis(2,4-bis(dimethylaminoethylimino)cyclodiphosph(V)azane (H2L2) and (1,3-dimethyl-2,4-dioxo-2'-(dimethylaminoethylimino)-4'-(dimethylaminopropyl-imino)cyclodiphosph(V)azane (H2L3) containing four active coordination centers (NNNN) and their Cu(II) complexes have been synthesized and characterized by elemental analyses, spectroscopic methods, molar conductance as well as thermal and magnetic measurements. The UV–Vis and mass spectra of the ligands and their Cu(II) complexes were also recorded. The copper(II) complexes were found to have magnetic moments of 1.58–1.69 B. M. corresponding to one unpaired electron. The possible geometries of the complexes were assigned on the basis of EPR, electronic, and infrared spectral studies. The absence of water molecules in all complexes was supported by thermal studies. All the thermal decomposition processes ended with the formation of CuO. The kinetic and thermodynamic parameters have been calculated. The ligand (H2L3) and its Cu(II) complexes were screened for their anticancer studies against human breast cancer cell lines MCF-7 and minimum inhibitory concentration was calculated. The screening was extended to the antibacterial activity using Kirby–Bauer single disk susceptibility test for all compounds.  相似文献   

17.
A novel naphthalenediol‐based bis(salamo)‐type tetraoxime compound (H4L) was designed and synthesized. Two new supramolecular complexes, [Cu3(L)(μ‐OAc)2] and [Co3(L)(μ‐OAc)2(MeOH)2]·4CHCl3 were synthesized by the reaction of H4L with Cu(II) acetate dihydrate and Co(II) acetate dihydrate, respectively, and were characterized by elemental analyses and X‐ray crystallography. In the Cu(II) complex, Cu1 and Cu2 atoms located in the N2O2 sites, and are both penta‐coordinated, and Cu3 atom is also penta‐coordinated by five oxygen atoms. All the three Cu(II) atoms have geometries of slightly distorted tetragonal pyramid. In the Co(II) complex, Co1 and Co3 atoms located in the N2O2 sites, and are both penta‐coordinated with geometries of slightly distorted triangular bipyramid and distorted tetragonal pyramid, respectively, while Co2 atom is hexa‐coordinated by six oxygen atoms with a geometry of slightly distorted octahedron. These self‐assembling complexes form different dimensional supramolecular structures through inter‐ and intra‐molecular hydrogen bonds. The coordination bond cleavages of the two complexes have occurred upon the addition of the H+, and have reformed again via the neutralization effect of the OH?. The changes of the two complexes response to the H+/OH? have observed in the UV–Vis and 1H NMR spectra.  相似文献   

18.
Potassium 1,3-bis(N-methyl piperazino)propan-2-O-xanthate (LK), and its complexes with Co(II), Ni(II) and Cu(I) ions have been prepared and characterized as [CoL2(H2O)2], [NiL2(H2O)2]·2H2O and CuL·2H2O by FT-IR, 1H and 13C?NMR spectroscopies, elemental analyses, magnetic susceptibility and TGA techniques.  相似文献   

19.
Three new branched hexadentate amines (N6), 3,6-bis(2-pyridylmethyl)-3,6-diazaoctane-1,8-diamine (1), 3,7-bis(2-pyridylmethyl)-3,7-diazanonane-1,9-diamine (2) and 3,8-bis(2-pyridylmethyl)-3,8-diazadecane-1,10-diamine (3) have been synthesized. Subsequently, three novel Schiff base macrocyclic complexes containing a phenanthroline and two 2-pyridylmethylpendant arms have been prepared by template [1+1] cyclocondensation of 2,9-dicarboxaldehyde-1,10-phenanthroline and the branched hexadentate amines (13), in the presence of Mn(II) in methanol. These complexes have ligands with 18-, 19- and 20-membered hexaaza macrocycles and two 2-pyridylmethyl pendant arms (L1, L2 and L3, respectively). All the complexes have been characterized by elemental analysis and IR spectroscopy. The crystal structure of [MnL1](ClO4)2 · 3CH3CN was determined and indicates that in the solid state the complex adopts a slightly distorted hexagonal bipyramidal geometry with the Mn(II) ion located within a hexaaza macrocycle with the two 2-pyridylmethyl pendant arms coordinating in axial positions.  相似文献   

20.
Abstract

The title compound [Cu3Br4C28H28N4O2] is a type of polymeric three-centre octahedral-trigonal planar coordination complex. The copper(II) atom located at a centre of symmetry is six-coordinate with two bidentate (N3, O1) ligands of acetone-1-naphthoylhydrazone forming the equatorial plane and two bromine ions in axial positions (Cul-Brl = 2.946(1)Å). The ligands are in trans positions. The Cu(I) atoms are in trigonal planar coordination by two bridging Br? ions (Cu2-Br2 = 2.412(1)Å, Cu2-Br2? = 2.407(2)Å) which connect two Cu(I) atoms and a third bromine ion shared with the octahedral Cu(II) ion (Cu2-Br1 = 2.304(1)Å). The arrangement forms an infinite chain along the b axis.  相似文献   

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