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1.
The complexes MLCl2 · nH2O and ML2Cl2 · nH2O, where M = Cu(II), Zn and n = 1–4, were isolated and identified due to the reactions of Cu(II) and Zn(II) chlorides with 2,4,7-trinitrofluorene (L1), 2,4,7-trinitrofluorenone (L1a), and 2,4,5,7-tetranitrofluorene (L2). It was shown that, during complex formation, L1 and L2 were oxidized to fluorenones (L1a, L2a) and as neutral ligands formed 1: 1 and 2: 1 complexes with metal cations. A single crystal of tetranitrofluorenone (L2a) was isolated, and its crystal and molecular structure was determined. The complexes were studied by X-ray powder diffraction analysis, their spectral (IR and UV) characteristics were determined, and the structures for the complexes were proposed.  相似文献   

2.
The behavior of potassium tetrachloropalladate(II) in media simulating biological fluids has been studied. In aqueous solutions of NaCl, the aquation rate is higher than the rate of chloro ligand introduction into the internal coordination sphere of palladium. In HCl solutions, on the contrary, the process of palladium chloro complex formation predominates. The latter is apparently due to protonation of water molecules composing aqua complexes. By means of the ZINDO/1 method, the substitution of ligands – water molecules and hydronium ion – in planar complexes of palladium(II) by chloride ion has been investigated. All complexes containing H2O and H3O+ ligands, other than [Pd(H2O)4]2+, have intramolecular hydrogen bonds. In [Pd(H2O)3(H3O)]3+ and trans-[Pd(H2O)2(H3O)Cl]2+, a “non-classic” symmetric hydrogen bond O ··· H ··· O is established (ZINDO/1, RHF/STO-6G*). By the first three steps the substitution of hydronium ion in the internal sphere of palladium atom is more favorable thermodynamically, compared to water molecules. Logarithms of stepwise stability constants of palladium(II) chloride complexes correlate linearly to enthalpies (ZINDO/1, PM3) of water substitution by chloride ion.  相似文献   

3.
A Schiff base (HCSmz) was synthesized via (E)-cinnamaldehyde with S-methyl dithiocarbazate and six bivalent transition metal complexes [M(CSmz)2] (M=Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+) were prepared. The complexes were characterized by elemental analyses, IR, 1H NMR, and UV-Vis spectra, and the Ni(II) and Zn(II) complexes were also characterized by single crystal X-ray diffraction. After tautomerism of thiotone to thioenol and deprotonization of the thioenol, two ligands chelate the metal by two nitrogens of azomethine and two sulfurs of thioenol. Ni(CSmz)2 crystallizes in the centrosymmetric space group P21 /n with a perfectly square planar trans-configuration with Ni located at the center of the square; crystal packing is stabilized by intra- and intermolecular C–H···S hydrogen bonds. Zn(CSmz)2 is in the mirror-symmetric space group I41 /a in a distorted tetrahedral geometry with two equivalent Zn–N and Zn–S bonds; crystal packing is stabilized by intermolecular C–H···π hydrogen bonds.  相似文献   

4.
Two new potentially hexadentate Schiff bases, [H2L1] and [H2L2], were prepared by condensation of 2-(3-(2-aminophenoxy)naphthalen-2-yloxy)benzenamine with 3,5-di-tert-butyl-2-hydroxy benzaldehyde and o-vanillin, respectively. Reaction of these ligands with cobalt(II) chloride, copper(II) perchlorate, and zinc(II) nitrate gave complexes ML. The ligands and their complexes have been characterized by a variety of physico-chemical techniques. The solid and solution state investigations show that the complexes are neutral. Molecular structures of [CuL1], [CoL1]?·?C7H8, and [ZnL2]?·?CH3CN, which have been determined by single-crystal X-ray diffraction, indicate that [CuL1] and [ZnL2]?·?CH3CN display distorted square planar and distorted trigonal-bipyramidal geometry, respectively; the geometry around cobalt in [CoL1]?·?C7H8 is almost exactly between trigonal bipyramidal and square pyramidal. The synthesized ligands and their complexes were screened for their antibacterial activities against eight bacterial strains and the ligands and complexes have antibacterial effects. The most effective ones are [CuL2] against Proteus vulgaris, Serratia marcescens, Staphylococcus subtilis, [H2L1] against S. subtilis, and [H2L2] against S. subtilis.  相似文献   

5.
Binuclear cobalt(II), nickel(II), copper(II) and zinc(II) complexes of general composition [M2L1-2(μ-Cl)Cl2] · nH2O with the Schiff-base ligands (where L1H and L2H are the potential pentadentate ligands derived by condensing 2,6-diformyl-4-methylphenol with 4-amino-3-antipyrine and 2-hydroxy-3-hydrazinoquinoxiline, respectively) have been synthesized and characterized. Analytical and spectral studies support the above formulation. 1H-NMR and IR spectra of the complexes suggest they have an endogenous phenoxide bridge, with chloride as the exogenous bridge atom. The electronic spectra of all the complexes are well characterized by broad d–d and a high intensity charge-transfer transitions. The complexes are chloro-bridged as evidenced by two intense far-IR bands centered around 270–280 cm−1. Magnetic susceptibility measurements show that complexes are antiferromagnetic in nature. The compounds show significant growth inhibitory activity against fungi Aspergillus niger and Candida albicans and moderate activity against bacteria Bacillus cirroflagellosus and Pseudomonas auresenosa.  相似文献   

6.
Three new vic-dioxime ligands, [N-(ethyl-4-amino-1-piperidine carboxylate)-phenylglyoxime (L1H2), N-(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L2H2), and N,N′-bis(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L3H2)], and their Co(II) with Cu(II) metal complexes, were synthesized for the first time. Mononuclear complexes of these ligands with a 1:2 metal-ligand ratio were prepared with Co(II) and Cu(II) salts. The BF2+-capped Co(II) and mononuclear complexes of the vic-dioxime were prepared for [Co(L1·BF2)2] and [Co(L2·BF2)2]. The ligands act in a polydentate fashion bonding through nitrogen atoms in the presence of a base, as do most vic-dioximes. The cobalt(II) and copper(II) complexes are non-electrolytes as shown by their molar conductivities (ΛM) in DMF. The structures of the ligands and complexes were determined by elemental analyses, FT-i.r., u.v.–vis., 1H- and 13C-n.m.r. spectra, magnetic susceptibility measurements, and molar conductivity. The comparative electrochemical studies show that the stabilities of the reduced or oxidized species and the electrode potentials of the complexes are affected by the substituents attached on the oxime moieties of the complexes.  相似文献   

7.
Two new ligands, 4-hydroxy coumarin-3-thiosemicarbazone (H2L1) and 4-hydroxy coumarin-3-semicarbazone (H2L2) were synthesized and used for the preparation of a series of transition metal complexes (Cr3+, Co2+, Ni2+, Cu2+, and Fe3+), derived from these ligands. These complexes have the forms [ML1Cl2nX (15) and [ML2Cl]·nX (69) (X = H2O or ethanol). The structures of these complexes were elucidated by elemental analyses, IR, UV–Vis, and electrical conductivity, as well as magnetic susceptibility measurements and thermal analyses. IR spectral data indicates that in all complexes, the ligands act as monobasic tridentate, coordinated through keto oxygen or sulfur, azomethine nitrogen and deprotonated phenolic oxygen atom. On the basis of other physicochemical investigations, tetrahedral or square planar geometries are assigned for Cu2+ complexes in monomeric structures. In the case of the Co2+, Ni2+ and Fe3+ complexes, octahedral stereochemistries in monomeric structures are suggested. The dissociation constants of the ligands and the stability constants of their Cu(II), Co(II), Ni(II), and Fe(III) complexes have been also determined using potentiometric pH-metric titration in mixed solvents of dioxane: H2O and DMF: H2O with different ratios and different temperatures.  相似文献   

8.
Six complexes, [VO(L1-H)2]?·?5H2O (1), [VO(OH)(L2,3?H)(H2O)]?·?H2O (2,3), [VO(OH)(L4,5?H)(H2O)]?·?H2O (4,5), [VO(OH)(L6?H)(H2O)]?·?H2O (6), were prepared by reacting different derivatives of 5-phenylazo-6-aminouracil ligands with VOSO4?·?5H2O. The infrared and 1H NMR spectra of the complexes have been assigned. Thermogravimetric analyses (TG, DTG) were also carried out. The data agree quite well with the proposed structures and show that the complexes were finally decomposed to the corresponding divanadium pentoxide. The ligands and their vanadyl complexes were screened for antimicrobial activities by the agar-well diffusion technique using DMSO as solvent. The minimum inhibitory concentration (MIC) values for 14 and 6 were calculated at 30°C for 24–48?h. The activity data show that the complexes are more potent antimicrobials than the parent ligands.  相似文献   

9.
To explore the coordination abilities of nitronyl nitroxide ligands, two ligands substituted with quinoxaline ( L1 ) and 2‐phenyl‐1, 2, 3‐triazole ( L2 ) and their NiII and ZnII complexes: Ni( L1 )(hfac)2 ( 1 ), Ni( L2 )(hfac)2 ( 2 ), and Zn( L2 )(hfac)2 ( 3 ) (hfac = hexafluoroacetylacetonate), were synthesized and characterized. X‐ray single‐crystal diffraction analysis shows that compound 1 has a mononuclear structure, which is further linked into a three‐dimensional (3D) supramolecular network by C–H ··· F hydrogen‐bonding, C–H ··· π, and π ··· π stacking interactions. Complexes 2 and 3 have similar mononuclear structures, which are further linked into one‐dimensional (1D) supramolecular chains by various intermolecular weak interactions, such as C–H ··· F hydrogen‐bonding, and π ··· π stacking interactions. The results indicate that the steric bulk of L1 and L2 and the existence of hexafluoroacetylacetonate (hfac) play important roles in controlling the formation of the final frameworks of complexes 1 – 3 . Moreover, the luminescent properties of the ligands and their complexes were investigated in detail.  相似文献   

10.
Four novel Schiff base ligands and their copper(II) complexes, [Cu(L1)2] (1), [Cu(L2)2] (2), [Cu(L3)2] (3), and [Cu(L4)2] (4), were synthesized and characterized by elemental analyses, FT-IR, and UV–Vis spectroscopy. The ligands were synthesized from the condensation of 2-methoxyethylamine with various salicylaldehyde derivatives (x-salicylaldehyde for HLn, x = H (n = 1), 5-Br (n = 2), 3-OMe (n = 3), and 4-OMe (n = 4)). The molecular structures of 1, 2, and 3 were determined by the single crystal X-ray diffraction technique. The redox behavior studies of the complexes in acetonitrile display the electronic effects of the groups on the redox potential. The antioxidant activity of the Schiff base ligands and their Cu(II) complexes was evaluated using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method and FRAP assay. Furthermore, the in vitro anticancer activity of compounds was screened, including MTT and migration assays against gastric cancer cell line (MKN-45). The results show that all ligands and complexes have antioxidant and anticancer activity in a concentration-dependent way.  相似文献   

11.
Metal Complexes with N2O2S2 Donor Set. Synthesis and Characterization of the Cobalt(II), Nickel(II), and Copper(II) Complexes of a 15‐ and a 16‐Membered Bis(2‐hydroxyethyl) Pendant Macrocyclic Ligand The macrocyclic ligands 6, 10‐bis(2‐hydroxyethyl)‐7, 8, 9, 11, 17, 18‐hexahydro‐dibenzo‐[e, n][1, 4, 8, 12]‐dithiadiaza‐cyclopentadecine ( 1 ) (L1) and 5, 13‐bis(2‐hydroxyethyl)‐7, 8, 9, 10, 16, 17, 18, 19, 20‐nonahydro‐dibenzo‐[g, o][1, 9, 5, 13]‐dithiadiaza‐cyclohexadecine (L4) have been prepared. They form the stable complexes [CoL1(‐H)CoL1](ClO4)3 ( 2 ), [NiL1](ClO4)2·MeOH ( 3 ), Λ‐[CuL1](ClO4)2·MeOH ( 4a ) and rac‐[CuL1](ClO4)2·MeOH ( 4b ), [NiL4](ClO4)2 ( 5 ), and [CuL4](ClO4)2 ( 6 ). The compounds 1 to 6 have been characterized by standard methods and single‐crystal X‐ray diffraction. In the complexes 2 to 6 the metal atoms are octahedrally coordinated by the N2O2S2 donor set of the ligands. L1 and L4 are folded herein along the N···M···S‐ and the N···M···N′‐axes, respectively. This results at the metal atom in a allcis‐configuration for the complexes of L1 and a trans‐N2cis‐O2cis‐S2‐configuration for the complexes of L4. The cobalt(II) complex 2 is a dimer, bridged by a rather short hydrogen bridge of 2.402(12)Å length. The copper(II) complexes of L1 and L4 differ with respect to the Jahn‐Teller‐distortion.  相似文献   

12.
Potentially tetradentate ligands N,N"-di(2-hydroxybenzyl)ethylenediamine (L1) and N,N"-di(2-hydroxybenzyl)o-phenylenediamine (L2) and complexes of Cu(II), Co(II), and Ni(II) with L1and L2were synthesized. The EPR and electronic spectroscopy methods were used to reveal the octahedral structure of the Cu(II) complex with L1in the solid state. In water–alcohol solutions, the Cu(II) and Ni(II) complexes with both ligands have distorted octahedral structures. The Co(II) complexes form dioxygen adduct with L1. In the presence of oxygen, the ligands in the obtained complex compounds can undergo oxidative dehydrogenation with selective formation of the respective disalicylaldimines. In the case of L2, the oxidative dehydrogenation is observed for the complexes of all studied metals in comparatively mild conditions (T= 30°C, methanol and other solvents), while in the case of L1, it occurs only with the Co(II) complexes in the presence of pyridine.  相似文献   

13.
Starting from their six-coordinate iron(II) precursor complexes [L8RFe(MeCN)]2+, a series of iron(III) complexes of the known macrocyclic tetracarbene ligand L8H and its new octamethylated derivative L8Me, both providing four imidazol-2-yliden donors, were synthesized. Several five- and six-coordinate iron(III) complexes with different axial ligands (Cl, OTf, MeCN) were structurally characterized by X-ray diffraction and analyzed in detail with respect to their spin state variations, using a bouquet of spectroscopic methods (NMR, UV/Vis, EPR, and 57Fe Mößbauer). Depending on the axial ligands, either low-spin (S=1/2) or intermediate-spin (S=3/2) states were observed, whereas high-spin (S=5/2) states were inaccessible because of the extremely strong in-plane σ-donor character of the macrocyclic tetracarbene ligands. These findings are reminiscent of the spin state patterns of topologically related ferric porphyrin complexes. The ring conformations and dynamics of the macrocyclic tetracarbene ligands in their iron(II), iron(III) and μ-oxo diiron(III) complexes were also studied.  相似文献   

14.
New chromium(III) complexes are synthesized by classical thermal and microwave (MW)-irradiated techniques. The Schiff bases 2-acetylfuran-S-benzyldithiocarbazate (L1H), 2-acetylthiophene-S-benzyldithiocarbazate (L2H), 2-acetylpyridine-S-benzyldithiocarbazate (L3H), and 2-acetylnaphthalene-S-benzyldithiocarbazate (L4H) were prepared by condensation of -S-benzyldithiocarbazate in ethanol with the respective ketones by using MW as well as conventional methods. The chromium(III) complexes have been prepared by mixing CrCl3 · 6H2O in 1 : 1 and 1 : 2 molar ratios with monofunctional bidentate ketimines. The structure of the ligands and their transition metal complexes were confirmed by elemental analysis, melting point determinations, molecular weight determinations, infrared (IR), electronic and electron paramagnetic resonance (EPR) spectral, and X-ray powder diffraction studies. On the basis of these studies it is clear that the ligands coordinated to the metal atom in a monobasic bidentate mode by S∩N donors. Thus, an octahedral environment around the chromium(III) has been proposed. The growth inhibiting potential of the ligands and complexes has been assessed against a variety of fungal and bacterial strains.  相似文献   

15.
Four different types of new ligands Ar[COC(NOH)R] n (Ar=biphenyl, n = 1 H2L1; Ar=biphenyl, n = 2 H4L2; Ar=diphenylmethane, n = 1 H2L3; Ar=diphenylmethane, n = 2 H4L4; R=2-amino-4-chlorophenol in all ligands) have been obtained from 1 equivalent of chloroketooximes Ar[COC(NOH)Cl] n (HL1-H2L4) and 1 equivalent of 2-amino-4-chlorophenol (for H2L1 and H2L3) or 2 equivalent of 2-amino-4-chlorophenol (for H4L2 and H4L4). (Mononuclear or binuclear cobalt(II), nickel(II), copper(II) and zinc(II) complexes were synthesized with these ligands.) These compounds have been characterized by elemental analyses, AAS, infra-red spectra and magnetic susceptibility measurements. The ligands have been further characterized by 1H NMR. The results suggest that the dinuclear complexes of H2L1 and H2L3 have a metal:ligand ratio of 1:2; the mononuclear complexes of H4L2 and H4L4 have a metal:ligand ratio of 1:1 and dinuclear complexes H4L2 and H4L4 have a metal:ligand ratio of 2:1. The binding properties of the ligands towards selected transition metal ions (MnII, CoII, NiII, CuII, ZnII, PbII, CdII, HgII) have been established by extraction experiments. The ligands show strong binding ability towards mercury(II) ion. In addition, the thermal decomposition of some complexes is studied in nitrogen atmosphere.  相似文献   

16.
Two new soluble vic-dioxime ligands, 4-isopropylanilineglyoxime (L1H2) and 4-benzylpiperidineglyoxime (L2H2) were prepared by reacting 4-isopropylaniline and 4-benzylpiperidine with anti-chloroglyoxime. Ten metal complexes were obtanied by reacting both ligands with Cu(II),Ni(II),Co(II), Zn(II), and Cd(II) cations. The ligands and their metal complexes were elucidated by elemental analysis, IR, UV-vis, 1H NMR, and 13C NMR and also magnetic moments of the complexes were determined. The text was submitted by the authors in English.  相似文献   

17.
The pendant‐armed ligands L1 and L2 were synthesized by N‐alkylation of the two secondary aminic groups of the oxaazamacrocyclic precursor L with o‐nitrobenzylbromide (L1) or p‐nitrobenzylbromide (L2). Metal complexes of L1 and L2 have been synthesized and characterized by microanalysis, MS‐FAB, conductivity measurements, IR, UV‐Vis, 1H and 13C NMR spectroscopy and magnetic studies. Crystal structures of ligands L1 and L2, as well as complexes [CdL1(NO3)2]·2CH3CN and [Ag2Br(L2)2](ClO4)·2CH3CN have been determined by single crystal X‐ray crystallography.  相似文献   

18.
Reactions of N-(2-hydroxy-3,5-R1,R2-benzyl)-4-aminoantipyrines with copper acetate in ethanol gave complexes with Schiff bases (SBs) rather than the expected complexes with reduced SBs; i.e., the starting ligands undergo oxidative dehydrogenation during the complexation reaction. The corresponding complexes with reduced SBs were obtained from sodium salts of the ligands and cupric sulfate in aqueous solutions. Kinetic measurements showed that oxidative dehydrogenation occurs in the heteroleptic complexes Cu(L i )(CH3COO)(X) (L i H are derivatives of N-(2-hydroxy-3,5-R1,R2-benzyl)-4-aminoantipyrines; i = 6–10; X = H2O, CH3OH, CH3CH2OH) but does not occur in the complexes CH3OH, CH3CH2OH. The absence of oxidative dehydrogenation of the ligands in Cu(L i )2 · H2O can be explained by the octahedral environment of the Cu2+ ion and, accordingly, the absence of the coordination site for molecular oxygen. The molecular structures of two Cu(II) complexes with SBs were determined by X-ray diffraction.  相似文献   

19.
Two new hexadentate N2O4 donor Schiff bases, H4L1 and H4L2, were synthesized by condensation of 4,6-diacetylresorcinol with glycine and alanine, respectively. The structures of the ligands were elucidated by elemental analyses, IR, 1H NMR, electronic, and mass spectra. Reactions of the Schiff bases with copper(II), nickel(II), and iron(III) nitrates in 1 : 2 molar ratio gave binuclear metal complexes and, in the presence of 8-hydroxyquinoline (8-HQ) or 1,10-phenanthroline (Phen) as secondary ligands (L′), mixed-ligand complexes in two molar ratios 1 : 2 : 2 and 1 : 2 : 1 (L1/L2 : M : L′). The complexes were characterized by elemental and thermal analyses, IR, electronic, mass, and ESR spectral studies, as well as conductivity and magnetic susceptibility measurements. The spectroscopic data reveal that the Schiff-base ligands were dibasic or tetrabasic hexadentate ligands. The coordination sites with the metal ions are two azomethine nitrogens, two oxygens of phenolic groups, and two oxygens of carboxylic groups. Copper(II) complexes were octahedral and square planar while nickel(II) and iron(III) complexes were octahedral. The Schiff bases, H4L1 and H4L2, and some of their metal complexes showed antibacterial activity towards Gram-positive (Staphylococcus aureus and Streptococcus pyogenes) and Gram-negative (Pseudomonas fluorescens and Pseudomonas phaseolicola) bacteria and antifungal activity towards the fungi Fusarium oxysporium and Aspergillus fumigatus.  相似文献   

20.
New complexes of type [Cu(HTBG)2]Cl2 (1), [Cu(TBG)2]·3H2O (2) and [CuL]·nH2O (3) L:L1, n = 2 and (4) L:L2, n = 1 (HTBG: 2-tolylbiguanide, L1 and L2: ligands resulted from 2-tolylbiguanide, ammonia/hydrazine and formaldehyde one pot condensation) were synthesised and characterised. The features of complexes have been assigned from microanalytical, IR and UV–Vis data. Redox behaviour was established by cyclic voltammetry. The in vitro qualitative and quantitative antimicrobial activity assays showed that the complexes exhibited variable antimicrobial activity against Gram-negative and Gram-positive strains isolated from the hospital environment. The thermal analyses have evidenced the thermal intervals of stability and also the thermodynamic effects that accompany them. After water elimination, complexes have a similar thermal behaviour. Processes as water elimination, melting, chloride anion removal as well as oxidative degradation of the organic ligands were observed. The final product of decomposition was copper (II) oxide.  相似文献   

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