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1.
Cobalt(II), nickel(II), and copper(II) complexes containing 5,12-di(4-bromophenyl)-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H2L1) and 5,12-diphenyl-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H2L2) have been synthesized. All complexes were characterized by elemental analysis, MALDI TOF-MS spectrometry, and electronic absorption spectroscopy. The crystal structures of two compounds, [Cu2(H2L1)Cl4]n and [NiL2], were determined by X-ray powder diffraction. In the polymeric [Cu2(H2L1)Cl4]n, the Cu2Cl4 units and H2L1 molecules are situated on inversion centers. Each Cu(II) has a distorted trigonal-bipyramidal coordination environment formed by N and O from H2L1 [Cu–N 2.340(14)?Å, Cu–O 1.952(11)?Å], two bridging chlorides [Cu–Cl 2.332(5), 2.279(5)?Å] and one terminal chloride [Cu–Cl 2.320(6)?Å]. In the [NiL2] complex, the Ni(II) situated on inversion center has a distorted square-planar coordination environment formed by four nitrogens from L2 [Ni–N 1.860(11), 1.900(11)?Å].  相似文献   

2.
Syntheses of nickel(II) complexes of the tetraaza macrocycles 2,7-dichloro-1,3,6,8-tetraazacyclodecane (DCCD) and 2,8-dichloro-1,3,7,9-tetraazacyclododecane (DICD) and a copper(II) complex of 2,6,8,12,13,17-hexaazabicyclo[5.5.5]heptadecane (HBCH) are reported in the template condensation of trichloromethane with 1,2-diaminoethane or 1,3-diaminopropane. Formulation of the synthesized products [Ni(DCCD)(H2O)2]Cl2, [Ni(DICD)(H2O)2]Cl2?·?H2O, and [Cu3(HBCH)(H2O)6]Cl6, and the metal-free ligand hydrochloride HBCH?·?6HCl has been confirmed by elemental analyses, conductivity measurements, and spectral studies. Potentiometric studies of nickel(II) and copper(II) complexes of HBCH and structurally similar 2,5,8,10,13,16,17,20,23-nonaazabicyclo[7.7.7]tricosane (NACT, earlier derived from trichloromethane and diethylenetriamine) have also been performed in the structural support of HBCH. In 1?:?1, metal?:?HBCH solution, copper(II) is coordinated to four N-donors of two-HN(CH2)3NH– groups of the ligand in a non-planar tetraaza cavity. The equilibrium constant value (log?K?=?15.41) for the reaction Cu2+?+?A???CuA2+ (A?=?HBCH) is in favor of the cyclic structure of the ligand. A high value (log?K?=?23.27) for corresponding reaction in the NACT system is due to conformational change in the ligand, where copper(II) organizes the macrocycle to form a nearly planar cavity in which the cation fits well.  相似文献   

3.
This contribution presents a selection of results obtained using spectrophotometric and potentiometric titrations. For several reasons, the investigated equilibria present particular challenges to traditional analysis techniques. Equilibrium constants and UV–vis absorption spectra for different ligands in the complexation process of Ni(II) with pyridoxamine (pm), pyridoxal (pl) and pyridoxine are reported. The gradual and cumulative stability constants occurring in aqueous solution are presented for all complexes studied. Additionally, crystal-field parameters were calculated for two nickel(II) complexes synthesized, [Ni(pm)2]Cl2 and [Ni(pl)2]Cl2, respectively. The minimum inhibitory concentration and minimal bactericidal/fungicidal concentration values for Ni(II) complexes studied were obtained at 25 °C for 24–48 h. The activity data show that the complexes are more potent antimicrobials than the parent ligands.  相似文献   

4.
Mononuclear nickel(II) complexes with two ONS donor thiosemicarbazone ligands {salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone [H2L1] and salicylaldehyde 3-tetramethyleneiminyl thiosemicarbazone [H2L2]} have been prepared and physico-chemically characterized. IR and electronic spectra of the complexes have been obtained. The thiosemicarbazones bind to the metal as dianionic ONS donor ligands in all the complexes except in [Ni(HL1)2] (1). In compound 1, the ligand is coordinated as a monoanionic (HL) one. The magnetic susceptibility measurements indicate that all the complexes are mononuclear and are diamagnetic. The complexes were given the formulae [Ni(HL1)2] (1), [NiL1py] (2), [NiL1α-pic] (3), [NiL1γ-pic] · H2O (4), [NiL2py] (5) and [NiL2γ-pic] (6). The structures of compounds 2 and 3 have been solved by single crystal X-ray crystallography and were found to be distorted square planar in geometry with coordination of azomethine nitrogen, thiolato sulfur, phenolato oxygen and pyridyl nitrogen atoms.  相似文献   

5.
Four new complexes of Au(III), Pd(II), Ni(II), and Cu(II) ions were synthesized, derived from a novel heterocyclic ligand (L) that has both triazole and tetrazole rings. The ligand synthesis was through successive steps to achieve both heterocyclic rings. The synthesized compounds were characterized using conventional techniques like infrared, ultra violet—visible and proton/carbon nuclear magnetic resonance spectroscopy, metal and thermal analyses, and molar conductivity. All complexes were suggested to have square planar geometry, gold, nickel, and palladium complexes were salts while copper neutral complexes have the chemical formulas; [AuL2]Cl.2H2O, [PdL2]Cl2.2H2O, [NiL2]Cl2.2H2O, and [CuL2]. The cytotoxic effect was studied on breast cancer cell line (MCF‐7 cell line) at different concentrations by using the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay method, for the ligand (L) and complexes. The results showed that gold(III) and nickel(II) complexes have the highest cytotoxicity among all compounds against cancer cell lines.  相似文献   

6.
Reactions between nickel(II) and copper(II) salts [M(L) n ](ClO4)2 [L: 2-(pyrazole-1-ylmethyl)pyridine; n = 3 for Ni(II) and n = 2 for Ni(II) and Cu(II)] and LiTCNQ or mixture of LiTCNQ/TCNQ and Et3NH(TCNQ)2 yielded [Ni(L)3](TCNQ)2 · H2O, [Ni(L)2(TCNQ)2], [Ni(L)3](TCNQ)3, [Ni(L)2(TCNQ)3], and [Cu(L)2(TCNQ)3] · 3H2O. These complexes were characterized by infrared, electronic absorption, variable temperature magnetic moments and electron paramagnetic studies. Magnetic moments increase with increase in temperature attributed to contribution from TCNQ, which has also been examined by electron paramagnetic resonance.  相似文献   

7.
New Co(II), Ni(II), and Cu(II) complexes were synthesized with the Schiff base ligand obtained by the condensation of sulfathiazole with salicylaldehyde. Their characterization was performed by elemental analysis, molar conductance, spectroscopic techniques (IR, diffuse reflectance and UV–Vis–NIR), magnetic moments, thermal analysis, and calorimetry (thermogravimetry/derivative thermogravimetry/differential scanning calorimetry), while their morphological and crystal systems were explained on the basis of powder X-ray diffraction results. The IR data indicated that the Schiff base ligand is tridentate coordinated to the metallic ion with two N atoms from azomethine group and thiazole ring and one O atom from phenolic group. The composition of the complexes was found to be of the [ML2]∙nH2O (M = Co, n = 1.5 (1); M = Ni, n = 1 (2); M = Cu, n = 4.5 (3)) type, having an octahedral geometry for the Co(II) and Ni(II) complexes and a tetragonally distorted octahedral geometry for the Cu(II) complex. The presence of lattice water molecules was confirmed by thermal analysis. XRD analysis evidenced the polycrystalline nature of the powders, with a monoclinic structure. The unit cell volume of the complexes was found to increase in the order of (2) < (1) < (3). SEM evidenced hard agglomerates with micrometric-range sizes for all the investigated samples (ligand and complexes). EDS analysis showed that the N:S and N:M atomic ratios were close to the theoretical ones (1.5 and 6.0, respectively). The geometric and electronic structures of the Schiff base ligand 4-((2-hydroxybenzylidene) amino)-N-(thiazol-2-yl) benzenesulfonamide (HL) was computationally investigated by the density functional theory (DFT) method. The predictive molecular properties of the chemical reactivity of the HL and Cu(II) complex were determined by a DFT calculation. The Schiff base and its metal complexes were tested against some bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis). The results indicated that the antibacterial activity of all metal complexes is better than that of the Schiff base.  相似文献   

8.

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   

9.
Two pyrazole-based polydentate ligands, 1,3-bis(5-methyl-3-phenylpyrazol-1-yl)-propan-2-ol (Hmppzpo) and 1,3-bis(5-methyl-3-p-isopropylphenylpyrazol-1-yl)-propan-2-ol (Hmcpzpo), have been synthesized. A third ligand, 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-2-ol (Hdmpzpo), has been synthetically modified. Seven new M(II) coordination compounds of general formula M2L2X2 (M?=?Zn, Ni; X?=?NO3 or ClO4; L?=?dmpzpo, mppzpo or mcpzpo) or MLX (M?=?Pd; L?=?dmpzpo; X?=?Cl) were synthesized and structurally characterized by elemental analysis and FT-IR analysis. The crystal structures of [Zn2(μ-dmpzpo-O,N,N′)2(NO3)2]?·?2H2O (1?·?2H2O), [Ni2(μ-dmpzpo-O,N,N′)2(CH3CN)2](ClO4)2 (2) and Pd(μ-dmpzpo-N,N′)Cl2 (4) were determined by single-crystal X-ray crystallography. The crystal structures show that complexes 1?·?2H2O and 2 are center-symmetric dinuclear compounds, with two metal ions bridged by two alkoxo groups and each metal ion with a distorted square-pyramidal environment. The palladium complex, 4, displayed square-planar coordination geometry around the Pd(II) ion with trans arrangement.  相似文献   

10.
Summary Copper(II) and nickel(II) complexes of triazacycloalkanes (pqr-cy), with p, q, r = 2–6, have been prepared and characterized by means of electronic and i.r. spectroscopy, and by magnetic measurements. With nickel(II) mononuclear octahedral complexes [Ni(pgr-cy)2](CI04)2 are formed, but for copper(II) mononuclear octahedral complexes were obtained only for 222-cy and 223-cy. The other ligands gave copper(II) complexes of the type [Cu(pgr-cy)CI]CIO4, [Cu(pgr-cy)OH]ClO4, Or [Cu(pgr-cy)CI1/2OH1/2]ClO4. The hydroxy complexes have low magnetic moments and binuclear hydroxy bridged structures are proposed.Ligand names: e.g. p = q = r = 2 is 1,4,7-triazacvclononane  相似文献   

11.
This work describes the preparation and characterisation of ruthenium(II) complexes of several ONS donor ligands in the form of ring-substituted 4-phenylthiosemicarbazones of salicylaldehyde and o-hydroxyacetophenone. Reactions of these thiosemicarbazone ligands with [Ru(PPh3)3]Cl2 in refluxing MeOH furnished ruthenium(II) complexes of general formula [Ru(PPh3)2(LH)Cl] where the ligands acted as monoanionic tridentate ONS donors attached to the ruthenium(II) acceptor centre through the deprotonated phenolic oxygen, thione sulphur and azomethine nitrogen.  相似文献   

12.
A series of polymeric cobalt(II), nickel(II), zinc(II) and cadmium(II) azido complexes with hydrazine of the type [M(N2H4)(H2O)(N3)Cl]n, [M(N2H4)(N3)2]n and [M(N2H4)2(N3)2]n have been prepared. These were characterized by elemental analyses, magnetic susceptibility measurements, electronic and IR spectra. The complexes are highly insoluble in polar and non polar solvents. All the complexes decompose with explosion at different temperatures between 100°C to 200°C. The magnetic moment and electronic spectral data for Co(II) and Ni(II) complexes suggest that the complexes have octahedral structure. The ligand-field parameters (10 Dq, B, β, β° and LFSE) have also been calculated for all Co(II) and Ni(II) complexes which indicate a significant covalent character of M-L bonds. The IR spectra of the complexes show that the azide group and hydrazine molecule both act as bidentate bridging ligands in [M(N2H4)(H2O)(N3)Cl]n and [M(N2H4)(N3)2]n type complexes but the azide group is terminally bonded to metal in all [M(N2H4)2(N3)2]n type complexes.  相似文献   

13.
Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO3)2, Cu(ClO4)2, Zn(ClO4)2, Ni(NO3)2 and PdCl2 gives complexes with stoichiometry [Cu(L)2(H2O)2](NO3)2, [Cu(L)2(H2O)2](ClO4)2, [Zn(L)2(H2O)2] (ClO4)2, [Ni(L)2(H2O)Cl](NO3) and PdLCl2. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)2(H2O)2](NO3)2, [Cu(L)2(H2O)2](ClO4)2, and [Zn(L)2(H2O)2](ClO4)2 were determined by X-ray crystallography. The cation complexes [M(L)2(H2O)2] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.  相似文献   

14.
Bis(N-alkyldithiocarbamato)nickel(II) complexes (1–5) [Ni(S2CNHR)2] (where R?=?Me, Et, n-Pr, i-Pr, n-Bu) were synthesized by the reaction of NiCl2?·?6H2O and the corresponding sodium salt of N-alkyldithiocarbamate in 1?:?2 molar ratio in aqueous medium. These bis(N-alkyldithiocarbamato)nickel(II) complexes (1–5) were characterized by elemental analysis, UV-Visible, IR, and 1H/13C-NMR spectroscopy. The crystallographic investigation of [Ni(S2CNH(n-Pr))2] (3) and [Ni(S2CNH(i-Pr))2] (4) revealed distorted square-planar geometry around nickel(II). The dithiocarbamates have anisobidentate coordination with nickel and the dithiocarbamates are trans.  相似文献   

15.
Four tridentate ONS ligands, namely 2-hydroxyacetophenonethiosemicarbazone (H2L1), the 2-hydroxyacetophenone Schiff base of S-methyldithiocarbazate (H2L2), the 2-hydroxy-5-nitrobenzaldehyde Schiff base of S-methyldithiocarbazate (H2L3), and the 2-hydroxy-5-nitrobenzaldehyde Schiff base of S-benzyldithiocarbazate (H2L4), and their complexes of general formula [Ni(HL1)2], [ML] (M?=?NiII or CuII; L?=?L1, L2, L3 and L4), [Co(HL)(L); L?=?L1, L2, L3 and L4] and [ML(B)] (M?=?NiII or CuII; L?=?L2 and L4; B?=?py, PPh3) have been prepared and characterized by physico-chemical techniques. Spectroscopic evidence indicates that the Schiff bases behave as ONS tridentate chelating agents. X-ray crystallographic structure determination of [NiL2(PPh3)] and [CuL4(py)] indicates that these complexes have an approximately square-planar structure with the Schiff bases acting as dinegatively charged ONS tridentate ligands coordinating via the phenoxide oxygen, azomethine nitrogen and thiolate sulfur atoms. The electrochemical properties of the complexes have been studied by cyclic voltammetry.  相似文献   

16.
The synthesis and characterization of mononuclear tetrakis‐aziridine nickel(II ) and copper(II ) complexes as well as of a dinuclear bis‐aziridine copper(II ) complex are described. The reactions of anhydrous MCl2 (M = NiII, CuII) with aziridine (= az = C2H4NH, C2H3MeNH, CH2CMe2NH) in CH2Cl2 at room temperature in a 1:5 and 1:2 molar ratio, respectively, afforded the tetrakis‐aziridine complexes [M(az)4Cl2] (M = Ni, Cu) or the dimeric bis‐aziridine complex [Cu(az)2Cl2]2. After purification, all of the complexes were fully characterized. The single crystal structure analysis revealed two different coordination modes. Whereas both nickel(II ) complexes can be classified as showing an elongated octahedral structure, copper(II ) complexes show either an elongated octahedral or a square pyramidal arrangement forming dimers with chlorido bridges in axial positions. Furthermore, the results of magnetic measurements of the nickel(II ) and copper(II ) compounds are presented.  相似文献   

17.
Using the X-ray structure of solid nitrosoguanidine (ngH), potential structures of its complex with aqueous nickel(II) were surmised. A single-crystal X-ray diffraction determination of the Ni(II) complex confirmed one of these configurations. The X-ray structural parameters were compared with the most stable gaseous configurations derived from ab initio-MO calculations. The lowest energy calculated configuration of the nickel(II) complex and the X-ray crystal structure are in excellent agreement. The neutral diamagnetic, planar, red-colored [bis(nitrosoguanidate)nickel(II)] complex, [Ni(ng)2]°, is nitrogen coordinated in the trans configuration. It is highly insoluble in all solvents investigated, and has essentially the same crystal symmetry and unit-cell dimensions as the free ligand. In ligand crystals, two molecules have four nitrogen atoms aligned in a plane such that they are suitable for coordination to a nickel ion (1.945, 2.064?Å), when it is at the 1/2,?1/2,?1/2 unit-cell position. Furthermore, the complexes stack, as in [Ni(dmg)2]°, placing the nickel ions in nearly perfect positions for weak metal–metal bonding between adjacent layers at the near optimum distance of 3.65(1)?Å. This results in a tight, linear macromolecule having low volatility and the extremely low solubility observed. As far as we are aware this is the first instance in which a ligand crystal structure is essentially the same as the complex it forms, with minor differences in bond distances, angles and torsion angles, and suggests some potentially unique properties and applications for this material.  相似文献   

18.
Three new copper(II) complexes [CuL1N3]2 (1), [CuL2N3] (2) and [CuL3N3] (3) with three very similar tridentate Schiff base ligands [HL1?=?6-diethylamino-3-methyl-1-phenyl-4-azahex-3-en-1-one, HL2?=?6-amino-3-methyl-1-phenyl-4-azahex-3-en-1-one and HL3?=?6-amino-3-methyl-1-phenyl-4-azasept-3-en-1-one] have been synthesized and structurally characterized by X-ray crystallography. In complex 1 half of the molecules are basal-apical, end-on azido bridged dimers and the remaining half are square-planar monomers whereas all the molecules in complexes 2 and 3 are monomers with square-planar geometry around Cu(II). A competition between the coordinate bond and H-bond seems to be responsible for the difference in structure of the complexes.  相似文献   

19.
Blue crystals of metal nitratocuprates(II), M3[Cu(NO3)4](NO3) (M = K ( I ), NH4 ( II ), Rb ( III )) and Cs2[Cu(NO3)4] ( IV ) were synthesized from Cu(NO3)2 · 3 H2O and MNO3 by heating at 100–140 °C during 3–12 h. X-ray single crystal structures for isotypic I and II reveal the presence of the [Cu(NO3)4]2– and NO3 anions and M+ cations. Structure IV contains [Cu(NO3)4]2– and Cs+. In structures I , II , and IV , Cu atoms have a square-planar coordination [CuO4] with short Cu–O distances of 1.92–2.00 Å, the oxygen atoms belonging to four different NO3 groups. Each coordinated NO3 group is a nonsymmetrical bidentate ligand with the second, longer Cu–O distance from 2.38 to 2.74 Å. Rubidium derivative III was shown to be isotypic to I on the basis of unit cell dimensions and symmetry. Eight-coordinate metal(II) environment in tetranitrates is compared for transition metals with different electronic configurations.  相似文献   

20.
Complexes of the type [M(pash)Cl] and [M(Hpash)(H2O)SO4] (M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpash = p-amino acetophenone salicyloyl hydrazone) have been synthesized and characterized by elemental analyses, molar electrical conductance, magnetic moments, electronic, ESR and IR spectra, thermal studies and X-ray powder diffraction. All the complexes are insoluble in common organic solvents and are non-electrolytes. The magnetic moment values and electronic spectra indicate a square-planar geometry for Co(II), Ni(II) and Cu(II) chloride complexes and spin-free octahedral geometry for the sulfato complexes. The ligand coordinates through >C=N–,–NH2 and a deprotonated enolate group in all the chloro complexes, and through >C=N–, >C=O and–NH2 in the sulfato complexes. Thermal analyses (TGA and DTA) of [Cu(pash)Cl] show a multi-step exothermic decomposition pattern. ESR spectral parameters of Cu(II) complexes in solid state at room temperature suggest the presence of the unpaired electron in d x 2 ? y 2 . X-ray powder diffraction parameters for [Cu(pash)Cl] and [Ni(Hpash)(H2O)SO4] correspond to tetragonal and orthorhombic crystal lattices, respectively. The complexes show a fair degree of antifungal activity against Aspergillus sp., Stemphylium sp. and Trichoderma sp. and moderate antibacterial activity against E. coli and Clostridium sp.  相似文献   

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