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1.
Preparation, crystal structures and magnetic properties of new heterodinuclear CuIIGdIII (1) and CuIITbIII (2) complexes [CuLn(L)(NO3)2(H2O)3MeOH]NO3·MeOH (where Ln = Gd, Tb) with the hexadentate Schiff-base compartmental ligand N,N′-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-diamine (H2L = C19H20N2O4Br2) (0) have been described. Crystal structure analysis of 1 and 2 revealed that they are isostructural and form discrete dinuclear units with dihedral angle between the O1Cu1O2 and O1Gd1/Tb1O2 planes equal to 2.5(1)° and 2.6(1)°, respectively. The variable-temperature and variable-field magnetic measurements indicate that the metal centers in 1 and 2 are ferromagnetically coupled (J = 7.89 cm−1 for 1). Crystal and molecular structure of the Schiff base ligand (0) has been also reported. The complex formation changes the conformation of Schiff base ligand molecule. 相似文献
2.
Ryosuke Harada 《Inorganica chimica acta》2005,358(3):489-496
In order to investigate the influence of ligand distortion on metal centers of porphyrin complexes, distorted vanadyl porphyrin complexes, VO(OPP) (OPP = 2,3,5,10,12,13,15,20-octaphenylporphinato) and VO(DPP) (DPP = 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphinato), have been prepared. In the crystal structures, VO(OPP) and VO(DPP) had a ruffled structure and a saddle-shaped structure, respectively. In addition, these complexes exhibited red shift and broadening of the absorption bands in the UV-Vis spectra and significant negative shifts of oxidation potentials of the porphyrin ligands in the cyclic voltammograms compared with those of the planar VO(TPP) (TPP = tetraphenylporphinato). These results indicate that the OPP and DPP complexes have the distorted structures both in solids and in solutions. The VO bond characters of VO(TPP), VO(OPP), and VO(DPP) do not show the significant difference in their crystal structures and resonance Raman spectra. This suggests that the distortion of porphyrin ligand little affects the Lewis acidity of the metal center. The non-planar porphyrin distortion gives the change of HOMO-LUMO gap. 相似文献
3.
The dinuclear V(V) complexes (VOL)2O (L = SAE (1), SAMP (2), SAP (3)) have been synthesized from VO(acac)2 and the corresponding tridentate ligands LH2 in methanol under reflux conditions and subsequent air oxidation in organic solvent. They have been characterized by IR and NMR spectroscopy, by thermogravimetric analysis, and by single crystal X-ray diffraction for 1 and 2. DFT calculations were carried out for a better understanding of the vibrational pattern, principally the V-O related vibrations. Complex [VO(SAP)]2O (3) catalyzes the epoxidation of cyclooctene by TBHP in water in the absence of any added solvent with good selectivity. 相似文献
4.
Makoto Handa Akira Suzuki Sadayuki Shoji Kuninobu Kasuga Kunihisa Sogabe 《Inorganica chimica acta》1995,230(1-2):41-44
A vanadyl complex with perfluorinate phthalocyanine, VOPcF16, was prepared. The monomer-dimer solvent dependence was confirmed based on the solvent effect for the Q-band position-that is, VOPcF16 exists as a monomer in a nonpolar solvent such as benzene, but dimerizes in a polar solvent such as acetone. Electron spin resonance data also supported the solvent dependence found. In addition, the substituent effect of fluorine atoms on the redox properties was investigated by measuring the cyclic voltammograms in dichloromethane. On the reduction side, three redox couples were observed, the first two of which were assigned as being due to the reduction of the phthalocyanine ring (to LUMO), whose potentials are 0.4–0.5 V higher than those of the tetra-t-butyl and octabutoxy derivatives, VOPc(t-Bu)4 and VOPc(O-n-Bu)8. 相似文献
5.
Diego Moreno Claudia Palopoli Sandra Signorella 《Journal of inorganic biochemistry》2010,104(5):496-502
Two new MnIII complexes Na[Mn(5-SO3-salpnOH)(H2O)] ⋅ 5H2O (1) and Na[Mn(5-SO3-salpn)(MeOH)] ⋅ 4H2O (2) (5-SO3-salpnOH = 1,3-bis(5-sulphonatosalicylidenamino)propan-2-ol, 5-SO3-salpn = 1,3-bis(5-sulphonatosalicylidenamino)propane) have been prepared and characterized. Electrospray ionization-mass spectrometry, UV-visible and 1H NMR spectroscopic studies showed that the two complexes exist in solution as monoanions [Mn(5-SO3-salpn(OH))(solvent)2]−, with the ligand bound to MnIII through the two phenolato-O and two imino-N atoms located in the equatorial plane. The E1/2 of the MnIII/MnII couple (−47.11 (1) and −77.80 mV (2) vs. Ag/AgCl) allows these complexes to efficiently catalyze the dismutation of , with catalytic rate constants 2.4 × 106 (1) and 3.6 × 106 (2) M−1 s−1, and IC50 values of 1.14 (1) and 0.77 (2) μM, obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutase assay, in aqueous solution of pH 7.8. The two complexes are also able to disproportionate up to 250 equivalents of H2O2 in aqueous solution of pH 8.0, with initial turnover rates of 178 (1) and 25.2 (2) mM H2O2 min−1 mM−1 catalyst−1. Their dual superoxide dismutase/catalase activity renders these compounds particularly attractive as catalytic antioxidants. 相似文献
6.
Pavel N. Nesterenko Ilia Ya. Levitin Marina V. Tsikalova Mark E. Vol'pin 《Inorganica chimica acta》1995,240(1-2):665-668
Reversed-phase (RP) chromatographic behaviour of a series of acid-sensitive cationic alkylcobalt(III) chelates with both [N2O] Schiff base and ethylenediamine has been studied. Their retention times depend on the water content of the mixed eluents in an unusual parabolic manner, which is ascribed to the biphylic nature of the structures in question. Optimal conditions for RP HPLC quantitative analysis of these rather labile organocobalt complexes have been developed. Their decomposition in solutions under ambient conditions has been surveyed using this technique. 相似文献
7.
Synthesis, structures and luminescent properties of new heterobimetallic Zn-4f Schiff base complexes
A series of new 3d-4f heterobimetallic Schiff base complexes of the general formula [Zn(μ-L2)Ln(NO3)3(H2O)n] (Ln = La 1, Nd 2, Gd 3, Er 4 and Yb 5; n = 1 or 2; H2L2 = N,N′-bis(3-methoxy-5-p-tolylsalicylidene)ethylene-1,2-diamine) are synthesized and characterized. Complexes 1, 2, 4 and 5 are structurally characterized by X-ray crystallography. The photophysical properties of these complexes are also investigated. At room temperature, complexes 1-5 exhibit similar solution absorption and emission spectra in the UV-Vis region. Furthermore, compounds 2, 4 and 5 exhibit solution emission corresponding to the lanthanide(III) ion in the near-infrared region at room temperature. The triplet state emission of the 3d-4f bimetallic complexes without energy transfer is also determined through the photophysical study of complex 3. 相似文献
8.
《Bioorganic & medicinal chemistry letters》2014,24(15):3559-3564
A novel series of Cu(II), Ni(II), Zn(II), Co(II), and Cd(II) complexes have been synthesized from the Schiff base. Structural features were determined by analytical and spectral techniques like IR, 1H NMR, UV–vis, elemental analysis, molar electric conductibility, magnetic susceptibility and thermal studies. The complexes are found to be soluble in dimethylformamide and dimethylsulfoxide. Molar conductance values in dimethylformamide indicate the non-electrolytic nature of the complexes. Binding of synthesized complexes with calf thymus DNA (CT DNA) was studied. There is significant binding of DNA in lanes 2, 3, and 5. Lanes 4 and 6 are showing more florescence when compared to the control indicating that these molecules are strongly bound to the DNA by inserting themselves between the two stacked base pairs and exhibiting their original property of fluorescence. Angiogenesis study has revealed that the compounds B-2, B-4 and B-5 have potent antitumor efficacy and activation of antiangiogenesis could be one of the possible underlying mechanisms of tumor inhibition. 相似文献
9.
Two sets of ligands, set-1 and set-2, have been prepared by mixing 1,3-diaminopentane and carbonyl compounds (2-acetylpyridine or pyridine-2-carboxaldehyde) in 1:1 and 1:2 ratios, respectively, and employed for the synthesis of complexes with Ni(II) perchlorate, Ni(II) thiocyanate and Ni(II) chloride. Ni(II) perchlorate yields the complexes having general formula [NiL2](ClO4)2(L = L1 [N3-(1-pyridin-2-yl-ethylidene)-pentane-1,3-diamine] for complex 1 or L2[N3-pyridin-2-ylmethylene-pentane-1,3-diamine] for complex 2) in which the Schiff bases are monocondensed terdentate, whereas Ni(II) thiocyanate results in the formation of tetradentate Schiff base complexes, [NiL(SCN)2] (L = L3[N,N′-bis-(1-pyridin-2-yl-ethylidine)-pentane-1,3-diamine] for complex 3 or L4 [N,N′-bis(pyridin-2-ylmethyline)-pentane-1,3-diamine] for complex 4) irrespective of the sets of ligands used. Complexes 5 {[NiL3(N3)2]} and 6 {[NiL4(N3)2]} are prepared by adding sodium azide to the methanol solution of complexes 1 and 2. Addition of Ni(II) chloride to the set-1 or set-2 ligands produces [Ni(pn)2]Cl2, 7, as the major product, where pn = 1,3-diaminopentane. Formation of the complexes has been explained by the activation of the imine bond by the counter anion and thereby favouring the hydrolysis of the Schiff base. All the complexes have been characterized by elemental analyses and spectral data. Single crystal X-ray diffraction studies confirm the structures of three representative members, 1, 4 and 7; all of them have distorted octahedral geometry around Ni(II). The bis-complex of terdentate ligands, 1, is the mer isomer, and complexes 4 and 7 possess trans geometry. 相似文献
10.
Harry Adams Neil A. Bailey Philippe Bertrand Simon R. Collinson David E. Fenton Simon J. Kitchen 《Inorganica chimica acta》1996,250(1-2):139-148
The cyclocondensation of 2,5-diformylthiophene and the amines N,N-bis-(2-aminoethyl)-2-phenylethylamine, N,N-bis-(2aminoethyl)-t-butyl-amine and N,N-bis-(2-aminoethyl)-t-butyl-amine in the presence of silver(I) salts yields homodinuclear bibracchial tetraimine Schiff base macrocyclic complexes. The structures of two such complexes are also reported. The complex Ag2L4(NO3)(PF6) (2) crystallises in the triclinic space group
, No. 2) and has unit-cell dimensions a = 12.834(6), B = 13.183(6), C = 14.588(7) Å, = 64.86(4), β = 79.77(4), γ = 69.44(3)° with Z = 2; there is a monodentate and singly bridging nitrate anion present and the Ag---Ag separation is 4.161 Å. The complex Ag2L4(CH3CN)2(BF4)2·CH3CN (9) crystallises in the triclinic space group
, No. 2) and has unit-cell dimensions a = 9.297(4), B = 12.985(3), C = 21.770(5) Å, = 91.570(10), β = 92.33(3), γ = 97.92(3) ° with Z = 2; there is a strongly bonded acetonitrile molecule coordinated to each silver atom and the Ag---Ag separation is 4.920 Å. 相似文献
11.
Hydrazone Schiff base-manganese(II) complexes: Synthesis, crystal structure and catalytic reactivity
Five dissymmetric tridentate Schiff base ligands, containing a mixed donor set of ONN and ONO were prepared by the reaction of benzhydrazide with the appropriate salicylaldehyde and pyridine-2-carbaldehyde and characterized by FT-IR, 1H and 13C NMR. The complexes of these ligands were synthesized by treating an ethanolic solution of the appropriate ligand and one equivalent Et3N with an equimolar amount of MnCl2 · 4H2O or alternatively by a more direct route in which an ethanolic solution of benzhydrazide was added to ethanolic solution of appropriate salicylaldehyde and MnCl2 · 4H2O solution to yield [MnCl(L1)(H2O)2], [Mn(L2)2(H2O)2], [MnCl(L3)], [MnCl(L4)] and [MnCl2(H2O)(L5)]. The hydrazone Schiff base ligands and their manganese complexes including HL1-4 and L5 (HL1 = benzoic acid (2-hydroxy-3-methoxy-benzylidene)-hydrazide, HL2 = benzoic acid (2,3-dihydroxy-benzylidene)-hydrazide, HL3 = benzoic acid (2-hydroxy-benzylidene)-hydrazide, HL4 = benzoic acid (5-bromo-2-hydroxy-benzylidene)-hydrazide, L5 = benzoic acid pyridine-2-yl methylene-hydrazide) were characterized on the basis of their FT-IR, 1H and 13C NMR, and molar conductivity. The crystal structures of HL1 and [MnCl2(H2O)L5] have been determined. The results suggest that the Schiff bases HL1, HL2, HL3, and HL4 coordinate as univalent anions with their tridentate O,N,O donors derived from the carbonyl and phenolic oxygen and azomethine nitrogen. L5 is a neutral tridentate Schiff base with N,N,O donors. ESI-MS for the complexes Mn-L2,3,5 provided evidence for the presence of multinuclear complexes in solution. Catalytic ability of Mn-L1-5 complexes were examined and found that highly selective epoxidation (>95%) of cyclohexene was performed by iodosylbenzene in the presence of these complexes and imidazole in acetonitrile. 相似文献
12.
Pavel Nesterenko Ilia Levitin Nina Chernoglazova Elena Paskonova Natalia Penner Marina Tsikalova 《Inorganica chimica acta》1998,280(1-2):295-301
The electrophoretic migration behavior of acid-sensitive cationic alkylcobalt(III) complexes with tridentate Schiff bases and amines as well as that of related ‘inorganic’ cobalt(III) chelates with tridentate and tetradentate Schiff bases was studied. A correlation of the electrophoretic mobility of the organocobalt complexes in question with their structure was established. An attempt to optimize the analytical procedures for capillary electrophoretic separation of these rather labile complex cations is outlined. Their decomposition in solutions under ambient conditions was surveyed using this technique. 相似文献
13.
A series of organotin(IV) complexes with Schiff base ligand pyruvic acid 3-hydroxy-2-naphthoyl hydrazone [R2SnLY]2, L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = CH3OH (1), R = n-C4H9, Y = N (2), R = PhCH2 (3), R = Ph, Y = CH3OH (4), R = Me, (5) and [R3SnLY], L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = H2O, (6), R = Ph (7), R = Me (8) have been synthesized. These complexes have been characterized by elemental analysis, IR, 1H and 119Sn NMR spectra. The crystal and molecular structure of complexes 1, 2 and 6 have been determined by X-ray single crystal diffraction. Results showed that complex 1 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. The complex 2 has a monoclinic structure and the central tin atom is rendered six-coordinate in octahedrally configuration with a planar of SnO3N unit and two apical aryl C atoms. And the whole structure consists of molecular units connected by weak intermolecular Sn?N and O-H?N interactions. In the complex 6, the central tin atom is five-coordinate in distorted trigonal-bipyramidal geometry. 相似文献
14.
Two copper(II) complexes, [Cu(qsal)Cl](DMF) (1) and [Cu2(qsalBr)2Cl2](DMF) (2), with tridentate Schiff base ligands, 8-(salicylideneamino)quinoline (Hqsal) and 8-(5-bromo-salicylideneamino)quinoline (HqsalBr), respectively, were synthesised and structurally characterized. Each copper(II) ion in the two complexes is in a distorted square pyramidal N2OCl2 environment. Complex 1 exists as a polymeric species via equatorial-apical chloride bridges, whereas 2 is a di-chlorido-bridged dinuclear complex, where each bridging chloride simultaneously occupies an in-plane coordination site on one copper(II) ion and an apical site on the other copper(II) ion. Variable-temperature magnetical susceptibility measurements on the two complexes in the temperature range 2-300 K indicate the occurrence of intrachain ferromagnetic (J = +6.58 cm−1) and intramolecular antiferromagnetical (J = −6.91 cm−1) interactions. 相似文献
15.
Five bis(3-aryl-6,6-dimethylcyclohexadienyl)ruthenium complexes (4a-4e) are prepared by reactions between di-μ-chlorodichlorobis[(1-3η:6-8η)-2,7-dimethyl-octadienyl]diruthenium and the corresponding dienes. The larger aryl substituents increase the barrier to rotation in 4a-4e relative to bis(3-methyl-6,6-cyclohexadienyl)ruthenium (5b). The activation parameters were determined by line-shape analysis for the exchange process in 4a: ΔG† (183 K), 8.0 ± 0.2 kcal/mol; ΔH†, 10.3 kcal/mol; and ΔS†, 13 cal/mol/K. The electronic effect of the aryl substituents on the cyclohexadienyl ligand on the oxidation potential of the complex are compared to the effect of methyl substituents. 相似文献
16.
P.M. Vimal Kumar 《Inorganica chimica acta》2011,375(1):84-92
The Schiff base ligand, 4-isopropylbenzaldehyde[N-(3-oxo-3,4-dihydro-2-quinoxalinyl)hydrazone] (Ipbh), the 1:1 condensation product of 4-isopropylbenzaldehyde and 2-hydroxy-3-hydrazinoquinoxiline, has been synthesized and characterized by X-ray crystallography. A series of complexes of Ipbh with Nickel(II), viz., [Ni(Ipbh)2]Cl2 (1), [Ni(Ipbh)2]Br2 (2), [Ni(Ipbh)2]I2 (3), [Ni(Ipbh)2·(CH3OH)2](NO3)2·(CH3OH)2 (4) and [Ni(Ipbh)2ClO4]ClO4 (5) have been synthesized. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, spectroscopic studies, magnetic susceptibility measurements and TG/DTA methods. The solid-state structure of the complex 4 was established by single crystal X-ray crystallography. In all the complexes, Ipbh acts as a bidentate NO chelating agent, coordinated to the metal ion through the imine nitrogen and quinoxaline oxygen. In complex 4, Nickel(II) is in a distorted octahedral environment with an identical set of donor atoms, N2O4, coming from two imine nitrogen and two quinoxaline oxygen atoms of two Ipbh moieties as well as two oxygen atoms of the two methanol molecules. The crystal packing of Ipbh and the complex 4 exhibits 1D and 2D supramolecular networks, respectively through different intermolecular hydrogen-bonding interactions. 相似文献
17.
Synthesis, structures, spectral and electrochemical properties of copper(II) complexes of sterically hindered Schiff base ligands 总被引:1,自引:0,他引:1
The Schiff base ligands 2-(2,6-diisopropylphenyliminomethyl)phenol H(L1), 5-diethylamino-2-(2,6-diisopropylphenyliminomethyl)phenol H(L2), 2,4-di-tert-butyl-6-(2,6-diisopropylphenyliminomethyl)phenol H(L3), 3-(2,6-diisopropylphenyliminomethyl)naphthalen-2-ol H(L4) and 4-(2,6-diisopropylphenyliminomethyl)-5-hydroxymethyl-2-methylpyridin-3-ol H(L5) have been synthesized by the condensation, respectively, of salicylaldehyde, 4-(diethylamino)salicylaldehyde, 3,5-di-tert-butylsalicylaldehyde, 2-hydroxy-1-napthaldehyde and pyridoxal with 2,6-diisopropylaniline. The copper(II) bis-ligand complexes [Cu(L1)2] 1, [Cu(L2)2] 2, [Cu(L3)2] 3, [Cu(L4)2] 4 and [Cu(L5)2] · CH3OH 5 of these ligands have been isolated and characterized. The X-ray crystal structures of two of the complexes [Cu(L1)2] 1 and [Cu(L5)2] · CH3OH 5 have been successfully determined, and the centrosymmetric complexes possess a CuN2O2 chromophore with square planar coordination geometry. The frozen solution EPR spectra of the complexes reveal a square-based CuN2O2 chromophore, and the values of g‖ and g‖/A‖ index reveal enhanced electron delocalization by incorporating the strongly electron-releasing -NEt2 group (2) and fusing a benzene ring on sal-ring (4). The Cu(II)/Cu(I) redox potentials of the Cu(II) complexes reveal that the incorporation of electron-releasing -NEt2 group and fusion of a benzene ring lead to enhanced stabilization of Cu(II) oxidation state supporting the EPR spectral results. The hydrogen bonding interactions between the two molecules present in the unit cell of 5a generate an interesting two-dimensional hydrogen-bonded network topology. 相似文献
18.
Arindam Mukherjee Indranil Rudra Munirathinam Nethaji 《Inorganica chimica acta》2004,357(4):1077-1082
Alkoxo-phenoxo bridged tetranuclear copper(II) complexes [Cu4L2(O2CC6H4-p-OH)2] (1) and [Cu4L2(O2CC6H4-o-OH)2] (2) containing pentadentate Schiff base ligand N,N′-(2-hydroxypropane-1,3-diyl)bis(salicylaldimine) (H3L) are prepared and structurally characterized. Crystal structures of the complexes show the covalent linkage between two {Cu2L(O2CR)}(R = C6H4-p-OH, C6H4-o-OH) units through the phenoxo atoms of the Schiff base ligand showing axial/equatorial bonding modes. The Cu(1)-O(2)-Cu(2) alkoxo bridge angle is 131° in 1 and 2. The pendant ortho- and para- OH groups of the three-atom bridging carboxylate ligands show no apparent bonding interactions with the metal or other group(s). The complexes show a d-d band near 635 nm in CH2Cl2. Variable temperature magnetic susceptibility measurements in the temperature range 300-18 K show antiferromagnetically coupled spin system. A theoretical fit of the magnetic data using exchange parameters J1 and J2 for the intradimer and interdimer units of the quasi-linear tetrameric core gave values as: J1=−132,J2=−72 cm−1 for 1 and J1=−167,J2=−67 cm−1 for 2. 相似文献
19.
Nabil S. Youssef Eman El-Zahany Alessandro Caselli Simone Fantauzzi 《Inorganica chimica acta》2009,362(6):2006-605
New transition metal complexes of CoII, CuII, NiII and VIVO with the Schiff base, HL, 3-acetylcoumarin-N(4)-phenylthiosemicarbazone have been prepared. Characterisation of the HL ligand and its complexes is also reported. Mass spectra and NMR assignments for the ligand, using COSY, NOESY homonuclear and HMQC and HMBC heteronuclear correlation techniques were carried out. Electronic and magnetic moments of the complexes indicate that the geometries of the metal centres are either distorted octahedral, square pyramidal, square planar or tetrahedral. The structures are consistent with the IR, UV-Vis, ESR, as well as conductivity and magnetic moments measurements. Cyclopropanation reactions of unactivated olefins by ethyldiazoacetate (EDA) in the presence of LCuIICl as catalyst proceed with excellent TON (up to 9625). 相似文献
20.
Synthesis and multi‐spectroscopic study on DNA‐binding,cleavage and biological properties of M(II) complexes based on N2O2 donor Schiff base ligand 下载免费PDF全文
A novel Schiff base, (S,Z)‐4‐(methylthio)‐2‐((3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)amino)butanoic acid (L) and four M(II) complexes (where M = Co, Cu, Ni and Zn) were synthesized and characterized. The DNA‐binding characteristics of the complexes were investigated using various spectroscopic methods and viscosity measurements. Analysis of the results suggests that all the complexes bind to calf thymus DNA via intercalation. Among the four, Cu(II) complex was found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. These complexes also exhibit good antioxidant activities against 2,2‐diphenyl‐1‐picrylhydrazyl radical. In vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents. 相似文献