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1.
A. Dei 《Inorganica chimica acta》1975,12(1):79-83
The open-chain, potentially, pentadentate, ligan 1,11-bis(dimethylamino)-3,6,9-trimethyl-3,6,9,-triazaundecane (Me7tetren) forms a series of metal complexes having the general formula [M(Me7tetren)]Y2 (Y = 1, M = Co, Ni; Y = ClO4, M = Co, Ni, Cu, Zn). On the basis of their physical properties, it is suggested that all these compounds contains isostructural five-coordinate [M(Me7tetren)]2+ cations, the ligand acting as pentadentate. These complexes react in solution with thiocyanate ion to give mono- and, with exception of copper(II), di-thiocyanato five- and six-co-ordinate derivatives. Mono-thiocyanato derivatives of cobalt(II), nickel(II) and zinc(II) have been isolated as tetraphenylborate salts. Cobalt(II) and nickel (II) di-thiocyanato derivatives have been also isolated. Results are discussed in terms of the steric requirements of the ligand and electronic properties of the metal ions. 相似文献
2.
Cobalt(II), nickel(II), copper(II) and zinc(II) complexes with 2-acetylthiophene benzoylhydrazone have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, electronic, IR, NMR and ESR spectral techniques. The molecular structures of ligand and its copper(II) complex have been determined by single crystal X-ray diffraction technique. The Cu(II) complex possesses a CuN2O2 chromophore with a considerable delocalization of charge. The structure of the complex is stabilized by intermolecular π–π stacking and C–H?π interactions. Hatbh acts as a monobasic bidentate ligand in all the complexes bonding through a deprotonated C–O− and >CN groups. Electronic spectral studies indicate an octahedral geometry for the Ni(II) complex while square planar geometry for the Co(II) and Cu(II) complexes. ESR spectrum of the Cu(II) complex exhibits a square planar geometry in solid and in DMSO solution. The trend g|| > g⊥ > 2.0023 indicates the presence of an unpaired electron in the dx2-y2 orbital of Cu(II). The electro-chemical study of Cu(II) complex reveals a metal based reversible redox behavior. The Ni(II) complex shows exothermic multi-step decomposition pattern of the bonded ligand. The ligand and its most of the metal complexes show appreciable corrosion inhibition properties for mild steel in 1 M HCl medium. [Co(atbh)2] complex exhibited the greatest impact on corrosion inhibition among the other compounds. 相似文献
3.
U. Casellato D. Fregona S. Sitran S. Tamburini P.A. Vigato 《Inorganica chimica acta》1985,110(3):161-167
A new heptadentate compartmental ligand has been synthesized by condensation of 3-formylsalicylic acid and 1,5-diamino-3-thiapentane in methanol (H4La). This Schiff base contains an inner N2SO2 and an outer O2O2 site and gives, by reaction with copper(II), nickel(II) and uranyl(VI) diacetate, mononuclear, homo- and heterobinuclear complexes. In the mononuclear copper and nickel complexes, the metal ion is in the inner N2SO2 site, while it is in the outer O2O2 for uranyl; a solvent molecule fills the fifth equatorial coordination position in this last complex. The physico-chemical properties of the compounds are discusscd on the basis of infrared, electronic and magnetic data and by comparison with the analogous complexes with the ligand obtained by reaction of 3- formylsalicylic acid and diethylenetriamine (H4Lb). The mononuclear copper and the heterodinuclear copper-uranyl complexes show anomalously low magnetic moments. 相似文献
4.
Masoud Salavati-Niasari 《Inorganica chimica acta》2009,362(10):3738-259
Some complexes containing “[Ni([18]py2N4)]2+, [Ni([20]py2N4)]2+, [Ni(Bzo2[18]py2N4)]2+ and [Ni(Bzo2[20]py2N4)]2+” were successfully prepared by the template synthesis of 2,6-diacetylpyridine with [bis(diamine)nickel(II)]; [Ni(N-N)2]2+; within the zeolite-Y. These complexes were entrapped in the supercage of Y-zeolite by a two-step process in the liquid phase: (i) inclusion of a Ni(II) precursor complex, [Ni(diamine)2]2+@NaY, and (ii) template synthesis of the nickel(II) precursor complex with 2,6-diacetylpyridine. The new complex nanoparticles entrapped within the zeolite-Y “[Ni([18]py2N4)]2+@NaY, [Ni([20]py2N4)]2+@NaY, [Ni(Bzo2[18]py2N4)]2+@NaY, [Ni(Bzo2[20]py2N4)]2+@NaY” were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV-Vis, XRD, BET, DRS). Analysis of the data indicates that the Ni(II) complexes are encapsulated within the zeolite-Y and exhibit different property from those of the free complexes, which can arise from distortions caused by steric effects due to the presence of sodium cations, or from interactions with the zeolite matrix. 相似文献
5.
The photoreactions of tris(2,2′-bipyridine)nickel(II) complex, Ni(II)(bpy3)2+ were studied and compared with that of the photoreactions of 2,2′-bipyridine ligand. Continuous photolysis of the complex shows that the photodecomposition corresponds to the absorption of light by the complex in the ligand centered excited state. Flash photolysis of the complex using a 248 nm excimer laser yields bipyridine cation radical and solvated electron as transients. Absorption spectra of the transient observed for the complex is found to be similar to that observed for the ligand on flash excitation using a 248 nm laser suggesting that the transients observed in the case of complex is due to the coordinated bipyridine in the complex. The formation of solvated electron is observed to be monophotonic and that of the bipyridine cation radical is found to be a biphotonic process. Significant change in Ni-N bond distance upon oxidation of Ni(bpy3)2+ ion when compared to that observed in nickel(II)tetraazamacrocyclic complexes suggests that the formation of the trivalent complex by photolysis is not favored for the Ni(bpy3)2+ ion and CTTS excited state in the complex is not observed in the present system. 相似文献
6.
Skyrianou KC Perdih F Papadopoulos AN Turel I Kessissoglou DP Psomas G 《Journal of inorganic biochemistry》2011,105(10):1273-1285
The nickel(II) complexes with the quinolone antibacterial agents oxolinic acid, flumequine, enrofloxacin and sparfloxacin in the presence of the N,N′-donor heterocyclic ligand 2,2′-bipyridylamine have been synthesized and characterized. The quinolones act as bidentate ligands coordinated to Ni(II) ion through the pyridone oxygen and a carboxylato oxygen. The crystal structure of [(2,2′-bipyridylamine)bis(sparfloxacinato)nickel(II)] has been determined by X-ray crystallography. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they bind to CT DNA with [(2,2′-bipyridylamine)bis(flumequinato)nickel(II)] exhibiting the highest binding constant to CT DNA. The cyclic voltammograms of the complexes have shown that in the presence of CT DNA the complexes can bind to CT DNA by the intercalative binding mode which has also been verified by DNA solution viscosity measurements. Competitive study with ethidium bromide (EB) has shown that the complexes can displace the DNA-bound EB indicating that they bind to DNA in strong competition with EB. The complexes exhibit good binding propensity to human or bovine serum albumin protein having relatively high binding constant values. The biological properties of the [Ni(quinolonato)2(2,2′-bipyridylamine)] complexes have been evaluated in comparison to the previously reported Ni(II) quinolone complexes [Ni(quinolonato)2(H2O)2], [Ni(quinolonato)2(2,2′-bipyridine)] and [Ni(quinolonato)2(1,10-phenanthroline)]. The quinolones and their Ni(II) complexes have been tested for their antioxidant and free radical scavenging activity. They have been also tested in vitro for their inhibitory activity against soybean lipoxygenase. 相似文献
7.
Two new nickel(II) complexes of the composition [Ni(cyclam)(Hdipic)2] · 2H2O (1) and [Ni(cyclam)(H2O)2][Ni(dipic)2] · 2.5H2O (2) (cyclam = 1,4,8,11-tetraazacyclotetradecane) have been prepared and structurally characterized by a combination of analytical, spectroscopic, thermogravimetric, and crystallographic methods. The structure of 1 shows that the central nickel(II) ion is coordinated axially by two monodentate Hdipic ligands. The discrete neutral complex 1 further extends its structure by hydrogen bonding interactions to form a one-dimensional supramolecule. The structure of 2 consists of two independent nickel(II) centers. Water molecules instead of dipic ligands prefer to coordinate to the Ni1 ion forming a divalent cation [Ni(cyclam)(H2O)2]2+. Two dipic ligands coordinate to the second Ni2 ion forming a divalent anion [Ni(dipic)2]2−. The divalent cations and anions are charge-balanced, resulting in a molecular salt. The divalent cations and anions are interconnected by multiple types of hydrogen bonding interactions. 相似文献
8.
9.
《Inorganica chimica acta》1987,128(1):81-85
Bis (difluoroboron - α - furilglyoximato) nickel (II), C20H12O8N4B2F4Ni, was prepared by cyclization of its hydrogen-bonded precursor with BF3·OEt2. The compound crystallizes in the space group P21/c with a = 11.162(2), b = 5.569(2), c = 19.527(3) Å, β = 100.08(1)°, U = 1195.1(3) Å3, and Z = 2. The structure was refined to an R value of 0.033 using 2371 unique reflections collected with a CAD4-SDP diffractometer system. Unlike the corresponding planar macrocyclic as well as hydrogen-bonded dimethylglyoximates, the title compound neither dimerizes not exhibits columnar stacked structure. The 14-member macrocycle is planar except the B atoms, and no metal-metal interactions are observed in this compound. The complexation and cyclization reactions were investigated using spectral data. The structure is compared with other macrocyclic complexes. 相似文献
10.
Ali Akbar Khandar Seyed Abolfazl Hosseini-Yazdi Seyed Amir Zarei 《Inorganica chimica acta》2005,358(11):3211-3217
Copper(II) and nickel(II) complexes of potentially N2O4 Schiff base ligands 2-({[2-(2-{2-[(1-{2-hydroxy-5-[2-phenyl-1-diazenyl]phenyl}methylidene)amino] phenoxy}ethoxy) phenyl]imino}methyl)4-[2-phenyl-1-diazenyl]phenol (H2L1) and 2-({[2-(4-{2-[(1-{2-hydroxy-5-[2-phenyl-1-diazenyl]phenyl}methylidene)amino] phenoxy}butoxy) phenyl]imino}methyl)4-[2-phenyl-1-diazenyl]phenol (H2L2) prepared of 5-phenylazo salicylaldehyde (1) and two various diamines 2-[2-(2-aminophenoxy)ethoxy]aniline (2) and 2-[4-(2-aminophenoxy)butoxy]aniline (3) were synthesized and characterized by a variety of physico-chemical techniques. The single-crystal X-ray diffractions are reported for CuL1 and NiL2. The CuL1 complex contains copper(II) in a near square-planar environment of N2O2 donors. The NiL2 complex contains nickel(II) in a distorted octahedral geometry coordination of N2O4 donors. In all complexes, H2L1 behaves as a tetradentate and H2L2 acts as a hexadentate ligand. Cyclic voltammetry of copper(II) complexes indicate a quasi-reversible redox wave in the negative potential range. 相似文献
11.
Copper(II) and nickel(II) complexes are prepared of potentially quadridentate ligands (LH3), N-{2-(2- hydroxyethylamino)ethyl}- (seeH3), N-{3-(2-hydroxy- ethylamino)propyl}- (steH3), and N-{2-(3-hydroxypropylamino)ethyl}-salicylamide (setH3). The nickel complexes Na[Ni(see)] and Na[Ni(set)]·1/2H2O are diamagnetic and square-planar, in which the ligands act as a quadridentate one coordinated through secondary amino-N, and deprotonated phenolic-O, alcoholic-O, and amido-N atoms. The three copper complexes Na [CuL]·H2O (L = see, ste, set) with a normal magnetic moment have a similar square-planar structure. In another type complexes Cu(LH)·H2O (LH = seeH, setH) an alcohol group is not deprotonated. Two isomers are present in Cu(seeH)·H2O: one has a normal and the other a subnormal magnetic moment. The difficulty of complex formation of steH3 may be attributed to an unfavourably fused 6-6-5 membered chelate ring with strain. 相似文献
12.
A binucleating potentially hexadentate chelating agent containing oxygen, nitrogen and sulfur as potential donor atoms (H2ONNO) has been synthesized by condensing α,α-xylenebis(N-methyldithiocarbazate) with 2,4-pentanedione. An X-ray crystallographic structure determination shows that the Schiff base remains in its ketoimine tautomeric form with the protons attached to the imine nitrogen atoms. The reaction of the Schiff base with nickel(II) acetate in a 1:1 stoichiometry leads to the formation of a dinuclear nickel(II) complex [Ni(ONNO)]2 (ONNO2− = dianionic form of the Schiff base) containing N,O-chelated tetradentate ligands, the sulfur donors remaining uncoordinated. A single crystal X-ray structure determination of this dimer reveals that each ligand binds two low spin nickel(II) ions, bridged by a xylyl group. The nickel(II) atoms adopt a distorted square-planar geometry in a trans-N2O2 donor environment. Reaction of the Schiff base with nickel(II) acetate in the presence of excess pyridine leads to the formation of a similar dinuclear complex, [Ni(ONNO)(py)]2, but in this case comprises five coordinate high-spin Ni(II) ions with pyridine ligands occupying the axial coordination sites as revealed by X-ray crystallographic analysis. 相似文献
13.
Wei Luo Xiang-Gao Meng Jiang-Feng Xiang Yun Duan Gong-Zhen Cheng Zhen-Ping Ji 《Inorganica chimica acta》2008,361(9-10):2667-2676
Four novel trinuclear copper(II)/nickel(II) complexes with four trianionic pentadentate ligands, N-(3-t-butylbenzoyl)-5-nitrosalicylhydrazide (H33-t-bbznshz), N-(3,5-dimethylbenzoyl)salicylhydrazide (H33,5-dmbzshz), N-(phenylacetyl)-5-bromosalicylhydrazide (H3pabshz) and N-(3-t-butylbenzoyl)salicylhydrazide (H33-t-bbzshz) have been synthesized and characterized by X-ray crystallography. These trinuclear compounds all have an M–N–N–M–N–N–M core formed by three metal ions and two ligands. The geometries of three Cu(II) ions in compound Cu3(3-t-bbznshz)2(H2O)(DMF)(py)2 · DMF (1) alternate between distorted square pyramidal and square planar, while in compound Cu3(3,5-dmbzshz)2(py)2 (2), they are all square planar. Three Ni(II) ions in compound Ni3(pabshz)2(DMF)2(py)2 (3) and Ni3(3-t-bbzshz)2(py)4 · 2H2O (4) follow square-planar/octahedral/square-planar coordination geometry. Compounds 1, 2 and 4 are bent trinuclear, with the bend angles of 156.4°, 141.49° and 127.1°, respectively, while the three nickel ions in compound 3 are strictly linear, with an angle of 180°. Studies on the trinuclear Ni(II) complexes show that the β-branched N-acylsalicylhydrazide ligands with sterically flexible Cα methylene groups are easier to yield linear trinuclear Ni(II) complexes, while α-branched N-acylsalicylhydrazides ligands tend to form bent trinuclear Ni(II) complexes. Antibacterial screening data indicate that the trinuclear Cu(II) compound 2 is more active than 1 and mononuclear Cu(II) compound, bent trinuclear Ni(II) compound 4 is more active than linear compound 3 and less active than tetranuclear nickel compound in the previous study. 相似文献
14.
U. Casellato D. Fregona S. Sitran S. Tamburini P. A. Vigato 《Inorganica chimica acta》1985,110(3):181-190
A new heptadentate compartmental ligand has been synthesized by condensation of 3-formylsalicylic acid and 1,5-diamino-3-thiapentane in methanol (H4La). This Schiff base contains an inner N2SO2 and an outer O2O2 site and gives, by reaction with copper(II), nickel(II) and uranyl(VI) diacetate, mononuclear, homo- and heterobinuclear complexes. In the mononuclear copper and nickel complexes, the metal ion is in the inner N2SO2 site, while it is in the outer O2O2 for uranyl; a solvent molecule fills the fifth equatorial coordination position in this last complex. The physico-chemical properties of the compounds are discusscd on the basis of infrared, electronic and magnetic data and by comparison with the analogous complexes with the ligand obtained by reaction of 3- formylsalicylic acid and diethylenetriamine (H4Lb). The mononuclear copper and the heterodinuclear copper-uranyl complexes show anomalously low magnetic moments. 相似文献
15.
Two new nickel(II) complexes with the composition [Ni(L+H)(CH3CN)2](ClO4)3 (1) and [Ni(L)(tp)]·6H2O (2), (L = 3,10-bis{3-(1-imidazolyl)propyl}-1,3,5,8,10,12-hexaazacyclotetradecane, tp = terephthalate) have been synthesized and structurally characterized by a combination of analytical, spectroscopic and X-ray diffraction methods. The structure of 1 consists of monomeric cations of the formula [Ni(L+H)(CH3CN)2]3+ and perchlorate ions. The nickel(II) ion is six-coordinate with bonds to the four nitrogen atoms of the macrocycle and two nitrogen atoms of the axial acetonitrile ligands. One of the protonated imidazole pendants of the macrocycle is hydrogen bonded to the imidazole group of the neighboring nickel(II) macrocycle, forming an undulated 1D supramolecule. Then, the two 1D supramolecular chains are further interconnected by C-H···π interactions between the methyl group of the acetonitrile ligand and one of the imidazole groups to form a 2D double stranded supramolecular polymer. In the structure of 2, the 1D coordination polymer is formed with nickel(II) macrocycles and bridging terephthalate ions, where each 1D chain is interconnected with π-π interactions of pendant imidazole moieties of the macrocycles, resulting in the formation of a 2D supramolecule. 相似文献
16.
The equilibria involving nickel(II), nickel(I) and nickel(0) in the presence of bidentate phosphine ligands in acetonitrile solution have been investigated by cyclic voltammetry, controlled-potential electrolysis, and spectrophotometry. The obtained results show that when both cone angles and PP distance make the diphosphine well-suited to act as a chelating ligand, only bis-chelate complexes of the type NiL2 are formed by nickel in all the three achieved oxidation states. Longer methylene chains interposed between the phosphorus atoms make the diphosphine less suited to act in a bidentate fashion, thus allowing lower-order complexes, e.g. NiLS2 (S = solvent), to be obtained for nickel in the +2 and +1 oxidation states. Evidence for the poor stability of the [NiILS2]+ complexes and for a higher-order complex of the type NiL3 for nickel(II) have also been obtained. The dependence of the reduction potentials on the nature of the diphosphine employed is discussed. 相似文献
17.
N-(2-Pyridyl)acetamide (aapH) complexes of palladium(II), cobalt(II), nickel(II), and copper(II) have been studied by means of magnetic susceptibilities, and infrared, electronic, and PMR spectra. In the octahedral complexes M(aapH)2X2(M = Co, Ni, Cu; X = Cl, Br, NCS, NO3), bidentate aapH is chelated through the pyridine-N and amid-O atomes, whereas in the square-planar Pd(aapH)2X2 (X = Cl, Br) unidentate aapH is coordinated through the pyridine-N atom alone. Under alkaline conditions aapH is deprotonated in the presence of palladium(II) to form Pd(aap)2·4H2O, aap being an anionic bidentate ligand and chelating through the pyridine-N and amide-O atoms. 相似文献
18.
《Inorganica chimica acta》1988,142(1):113-117
It is generally accepted that copper(II) complexes involving 2-aminoethanol or a Schiff base deriving from this aminoalcohol display a tetranuclear structure with a Cu4O4 ‘cubane’ core. Using a Schiff base obtained by reacting 2′-aminoacetophenone with 2-aminoethanol, we have prepared copper(II) and nickel(II) complexes whose properties are fully consistent with a dinuclear structure. The copper complex is characterized by a low antiferromagnetic interaction. 相似文献
19.
Julieta Gradinaru Yurii Simonov Sandro Zecchin David E Fenton 《Inorganica chimica acta》2004,357(9):2728-2736
Four new square-planar Ni(II) and Cu(II) complexes with [N2O2] binding system were synthesized by metal-directed condensation of 2,6-diformyl-4-methylphenol with benzoyl or acetylacetone mono-S-methylisothiosemicarbazone. Only mononuclear “one-armed” complexes were obtained as a consequence of the different reactivity of the two carbonyl groups in the hydroxydialdehyde. The complexes were characterized by elemental analysis, EI MS and UV-Vis spectroscopy. The structural assignment was confirmed by X-ray diffraction analysis and NMR spectroscopy, for the Ni(II) complexes, and by ESR spectroscopy and magnetic measurements, for the Cu(II) complexes. 相似文献
20.
The crystal and molecular structures of the N-rac-isomer of the nickel(II) complex of 14-membered amide-containing macrocycle [NiL1] · 4H2O (H2L1=5,12-dioxo-1,4,8,11-tetraazacyclotetradecane) have been determined. Two deprotonated amide and two amine donors co-ordinate to the nickel(II) in nearly square planar manner with Ni-Namine bonds longer than Ni-Namide ones (1.930 vs. 1.898 Å). Water molecules do not co-ordinate and form hydrogen bond bridges between macrocyclic units in the crystal lattice. The analysis of 1H NMR data confirmed that the solid-state conformation of the macrocycle in N-rac[NiL1] is retained in aqueous solution though equilibrated with some amount of N-meso isomer. The comparison of the spectroscopic characteristics of the M(II) and M(III) complexes and the redox potentials of M(III/II) couples (M=Ni and Cu) for ML1 with those for ML2(H2L2=5,7-dioxo-1,4,8,11-tetraazacyclotetradecane) revealed a rather small influence of the trans- vs. cis-arrangement of amide donors in co-ordination spheres of the metal ions. 相似文献