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Bazzicalupi C Bencini A Bianchi A Duce C Fornasari P Giorgi C Paoletti P Pardini R Rosaria Tinè M Valtancoli B 《Dalton transactions (Cambridge, England : 2003)》2004,(3):463-469
The coordination properties of the ditopic oxa-aza macrocycles L1-L3 toward Ni(II) and Co(II) have been investigated by means of potentiometric and UV-vis spectrophotometric measurements. L1-L3 contain two triamine and/or tetraamine chains separated by two dioxa chains and form both mono- and dinuclear complexes in aqueous solution. In the [ML]2+ complexes, the metal ion is coordinated by one of the two polyamine moieties, while the other does not participate in the coordination. In the dinuclear complexes each metal ion is coordinated, almost independently, to a single polyamine moiety. Under aerobic conditions the binuclear Co(II) complexes of the ligands L1-L3 are able to bind molecular oxygen, with a bridging coordination of O2 between the two metals. 相似文献
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Singh BK Jetley UK Sharma RK Garg BS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,68(1):63-73
A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML(2) composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties. 相似文献
4.
Nair MS Joseyphus RS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(4):749-753
Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from vanillin and dl-alpha-aminobutyric acid were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements, powder XRD and biological activity. The analytical data show the composition of the metal complex to be [ML(H(2)O)], where L is the Schiff base ligand. The conductance data indicate that all the complexes are non-electrolytes. IR results demonstrate the tridentate binding of the Schiff base ligand involving azomethine nitrogen, phenolic oxygen and carboxylato oxygen atoms. The IR data also indicate the coordination of a water molecule with the metal ion in the complex. The electronic spectral measurements show that Co(II) and Ni(II) complexes have tetrahedral geometry, while Cu(II) complex has square planar geometry. The powder XRD studies indicate that Co(II) and Cu(II) complexes are amorphous, whereas Ni(II) and Zn(II) complexes are crystalline in nature. Magnetic measurements show that Co(II), Ni(II) and Cu(II) complexes have paramagnetic behaviour. Antibacterial results indicated that the metal complexes are more active than the ligand. 相似文献
5.
Ye QZ Xie SX Huang M Huang WJ Lu JP Ma ZQ 《Journal of the American Chemical Society》2004,126(43):13940-13941
Methionine aminopeptidase (MetAP) enzymes require a divalent metal ion such as Mn(II), Fe(II), Co(II), Ni(II), or Zn(II) for its removal of the N-terminal methionine from newly synthesized proteins, but it is not certain which of these ions is most important in vivo. Metalloform-selective MetAP inhibitors could be valuable for defining which metals are physiologically relevant for MetAP activation and could serve as leads for development of new therapeutic agents. We have screened a library of 43 736 small drug-like molecules against Escherichia coli MetAP and identified two groups of potent and highly metalloform-selective inhibitors of the Co(II)-form, and of the Mn(II)-form, of this enzyme. Compound 1 is 790-fold more selective for the Co(II)-form, while compound 4 is over 640-fold more potent toward the Mn(II)-form. The X-ray structure of a di-Mn(II) form of E. coli MetAP complexed with the Mn(II)-form-selective compound 4 was obtained, and it shows that the inhibitor interacts with both Mn(II) ions through the two oxygen atoms of its free carboxylate group. The preferential coordination of the hard (oxygen) donors to Mn(II) may contribute to its superb selectivity toward the Mn(II)-form. 相似文献
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Coronado E Galán-Mascarós JR Gómez-García CJ Murcia-Martínez A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(13):3484-3492
A new series of layered magnets with the formula [M(L-tartrate)] (M = Mn(II), Co(II), Fe(II), Ni(II); L-tartrate = (2R,3R)-(+)-tartrate) has been prepared. All of these compounds are isostructural and crystallize in the chiral orthorhombic space group I222, as found by X-ray structure analysis. Their structure consists of a three-dimensional polymeric network in which each metal shows distorted octahedral coordination bound to four L-tartrate ligands, two of which chelate through an alcohol and a carboxylate group and the other two bind terminally through a monodentate carboxylate group. The chirality of the ligand imposes a Delta conformation on all metal centers. Magnetically, the paramagnetic metal centers form pseudotetragonal layers in which each metal is surrounded by four other metals, with syn,anti carboxylate bridges. These salts show intralayer antiferromagnetic or ferromagnetic interactions, depending on the electronic configuration of the metal, and weak interlayer antiferromagnetic interaction. In all cases the magnetic properties are strongly affected by the anisotropy of the system, and the presence of magnetic canting has been found. The Mn derivative behaves as a weak ferromagnet with a critical temperature of 3.3 K. The Ni derivative shows very unusual magnetic behavior in that it exhibits antiferromagnetic ordering below 6 K, the onset of spontaneous magnetization arising from spin reorientation into a canted phase below 4.5 K, and a field-induced ferromagnetic state above 0.3 T at 2 K, behavior typical of metamagnets. The Fe and Co derivatives show antiferromagnetic interactions between spin carriers, but do not order above 2 K. 相似文献
8.
Al-Shaalan NH 《Molecules (Basel, Switzerland)》2011,16(10):8629-8645
The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II), Ni(II), Co(II), Mn(II), UO(2) (VI) and Fe(II) to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II), Ni(II) and UO(2) (VI) complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II) complex has a square-planar geometry distorted towards tetrahedral, the Ni(II) complex is octahedral while the UO(2) (VI) complex has its favoured heptacoordination. The Co(II), Mn(II) complexes and also other Ni(II) and Fe(III) complexes, which were obtained in the presence of Li(OH) as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and fungi (Candida albicans). The tested compounds exhibited high antibacterial activities. 相似文献
9.
《Polyhedron》1987,6(7):1517-1521
Formation constants of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with 3-hydroxy-2-naphthalene carboxylic acid have been determined potentiometrically in a 50% (v/v) dioxane—water solution at 25°C and 0.2 M KNO3. Experimental data are analysed using several computer programs. The obtained values for the log of the formation constant of the first 1 : 1 (metal : ligand) complex with the different metals are: Co 7.9, Ni 7.1, Cu 10.44, Zn 7.8 and Cd 7.3. The log of the formation constant for the 1 : 2 copper complex is 18.20. It is to be noted that Ni(II) yields a 1 : 1 complex weaker than expected from the Irving—Williams series. 相似文献
10.
V. V. Yanilkin N. I. Maksimyuk E. I. Gritsenko Yu. M. Kargin B. M. Garifullin 《Russian Chemical Bulletin》1992,41(2):217-222
A study has been made of the influence of Co(II) and Ni(II) ions on the kinetics of the homogeneous reduction of gem-dichlorocyclopropanes by anthracene anion radicals. It has been shown that Co(II) and Ni(II) ions accelerate this process. The observed effect depends on the nature and concentration of the metal ion and also on the type of gem-dichlorocyclopropane. Two mechanisms are examined: 1) homogeneous reduction of metal ions by anthracene anion radicals with the formation of univalent and zero-valent metals that are more effective reducting agents; and 2) activation of a dichlorocyclopropane molecule by previous coordination with a metal ion.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 292–297, February, 1992. 相似文献
11.
Pandey S Das PP Singh AK Mukherjee R 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10758-10768
Using an acyclic hexadentate pyridine amide ligand, containing a -OCH(2)CH(2)O- spacer between two pyridine-2-carboxamide units (1,4-bis[o-(pyrydine-2-carboxamidophenyl)]-1,4-dioxabutane (H(2)L(9)), in its deprotonated form), four new complexes, [Co(II)(L(9))] (1) and its one-electron oxidized counterpart [Co(III)(L(9))][NO(3)]·2H(2)O (2), [Ni(II)(L(9))] (3) and [Cu(II)(L(9))] (4), have been synthesized. Structural analyses revealed that the Co(II) centre in 1 and the Ni(II) centre in 3 are six-coordinate, utilizing all the available donor sites and the Cu(II) centre in 4 is effectively five-coordinated (one of the ether O atoms does not participate in coordination). The structural parameters associated with the change in the metal coordination environment have been compared with corresponding complexes of thioether-containing hexadentate ligands. The μ(eff) values at 298 K of 1-4 correspond to S = 3/2, S = 0, S = 1 and S = 1/2, respectively. Absorption spectra for all the complexes have been investigated. EPR spectral properties of the copper(II) complex 4 have been investigated, simulated and analyzed. Cyclic voltammetric experiments in CH(2)Cl(2) reveal quasireversible Co(III)-Co(II), Ni(III)-Ni(II) and Cu(II)-Cu(I) redox processes. In going from ether O to thioether S coordination, the effect of the metal coordination environment on the redox potential values of Co(III)-Co(II) (here the effect of spin-state as well), Ni(III)-Ni(II) and Cu(II)-Cu(I) processes have been systematically analyzed. 相似文献
12.
Here we report the syntheses and crystal structures of a series of cobalt(II) and nickel(II) complexes derived from (R)NP2 ligands (where R = OMe(Bz), H(Bz), Br(Bz), Ph) bearing ethylene linkers between a single N and two P donors. The Co(II) complexes generally adopt a tetrahedral configuration of general formula [(NP2)Co(I)(2)], wherein the two phosphorus donors are bound to the metal center but the central N-donor remains unbound. We have found one case of structural isomerism within a single crystal structure. The Co(II) complex derived from (Bz)NP2 displays dual coordination modes: one in the tetrahedral complex [((Bz)NP2)Co(I)(2)]; and the other in a square pyramidal variant, [((Bz)NP2)Co(I)(2)]. In contrast, the Ni(II) complexes adopt a square planar geometry in which the P(Et)N(Et)P donors in the ligand backbone are coordinated to the metal center, resulting in cationic species of formula [((R)NP2)Ni(I)](+) with iodide as counterion. All Ni(II) complexes exhibit sharp (1)H and (31)P spectra in the diamagnetic region. The Co(II) complexes are high-spin (S = 3/2) in the solid state as determined by SQUID measurements from 4 to 300 K. Solution electron paramagnetic resonance (EPR) experiments reveal a high-spin/low-spin Co(II) equilibrium that is dependent on solvent and ligand substituent. 相似文献
13.
The thermal stabilities of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) were studied in air and
nitrogen atmospheres. The complexes were obtained as mono-, di-, tetra-and pentahydrates with a metal to ligand ratio of 1:2
and with colours typical for M2+ ions (Mn-slightly pink, Co-pink, Ni-green, Cu-blue and Zn-white) and as polycrystalline compounds. When heated they dehydrate
to form anhydrous salts which nextare decomposed to the oxides of the respective metals in air while in nitrogen to the mixtures
of metal oxides and oxychlorides and carbon. The most thermally stable in air, nitrogen and argon atmospheres is 5-chloro-2-methoxybenzoate
of Cu(II) while the least thermally stable is that of Co(II).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
14.
Mixed ligand complexes of Cu(II), Ni(II), Co(II) and Zn(II) formed with glycine and uracil or 2-thiouracil have been synthesized and characterized by elemental analysis, conductance, spectral (IR and electronic spectra) and magnetochemical measurements. Results show that glycine is bidentate in all cases; uracil behaves as a bidentate ligand in Cu(II) complex, coordinating through its one carbonyl oxygen and nitrogen, whereas in other cases it is only monodentate, coordinating only through nitrogen. With thiouracil, coordination occurs from carbonyl oxygen and one nitrogen in Cu(II) and Ni(II) complexes, but in the Co(II) complex coordination occurs from thionyl sulphur and nitrogen. In the Zn(II) complex it shows tridentate behaviour, coordinating through oxygen, sulphur and one nitrogen. Mixed Cu(II), Co(II) and Zn(II) complexes of uracil and of Ni(II) and Zn(II) with thiouracil are octahedral, whereas the mixed Ni(II) complex with uracil shows distorted tetrahedral geometry, and the mixed Co(II)-thiouracil complex is square planar. The mixed Cu(II)-thiouracil complex has a binuclear structure, with square planar arrangement around each copper atom. 相似文献
15.
The hippurates of Co(II), Ni(II), Cu(II) and Zn(II) were isolated from the solution, their quantitative composition and the way of coordination of metal — ligand were determined and the conditions and products of thermal decomposition during heating in air atmosphere up to 1273 K were studied. The complexes of Ni(II), Cu(II) and Zn(II) heated lose some water molecules and then decompose to MO. The hippurate of Co(II) heated loses some water molecules and then decomposes to CoO with intermediate formation Co3O4.
Zusammenfassung Aus Lösung wurden die Co(II)-, Ni(II)-, Cu(II)- und Zn(II)-Salze der Hippursäure gewonnen, ihre quantitative Zusammensetzung sowie die Art der Koordination der Metall-Ligandenbindung bestimmt. Weiterhin wurden die Bedingungen und Produkte der thermischen Zersetzung beim Erhitzen in einer Luftatmosphäre bis 1273 K untersucht. Die Komplexe von Ni(II), Cu(II) und Zn(II) verlieren beim Erhitzen ein paar Moleküle Wasser und zersetzen sich anschlieend zu MO. Co(II)-hippurat gibt beim Erhitzen einige Moleküle Wasser ab und zersetzt sich dann über die Zwischenstufe Co3O4 zu CoO.相似文献
16.
Mononuclear Ni(II), Co(II), and Zn(II) complexes of the bppppa (N,N-bis[(6-phenyl-2-pyridyl)methyl]-N-[(6-pivaloylamido-2-pyridyl)methyl]amine) ligand have been synthesized and characterized by X-ray crystallography, 1H NMR, UV-vis (Ni(II) and Co(II)) and infrared spectroscopy, and elemental analysis. Each complex has the empirical formula [(bppppa)M](ClO4)2 (M = Ni(II), 2; Zn(II), 3; Co(II), 4) and in the solid state exhibits a metal center having a coordination number of five; albeit, the cation of 2 also has a sixth weak interaction involving a perchlorate anion. Treatment of [(bppppa)Ni](ClO4)2 (2) with 1 equiv of acetohydroxamic acid results in the formation of [(bppppa)Ni(HONHC(O)CH3)](ClO4)2 (1), a novel Ni(II) complex having a coordinated neutral acetohydroxamic acid ligand. In 1, one phenyl-appended pyridyl donor of the bppppa chelate ligand is dissociated from the metal center and acts as a hydrogen bond acceptor for the hydroxyl group of the bound acetohydroxamic acid ligand. Treatment of 1 with excess water results in the formation of 2 and free acetohydroxamic acid. We hypothesize that this reaction occurs due to disruption of the intramolecular hydrogen bonding interaction involving the bound acid. In this series of reactions, the bppppa ligand exhibits behavior reminiscent of a type III hemilabile ligand in terms of one phenylpyridyl donor. Treatment of 3 or 4 with acetohydroxamic acid results in no reaction, indicating that the bppppa-ligated Ni(II) derivative 2 exhibits unique coordination chemistry with respect to reaction with acetohydroxamic acid within this series of complexes. We attribute this reactivity to the ability of the bppppa-ligated Ni(II) center to adopt a pseudo-octahedral geometry, whereas the Zn(II) and Co(II) complexes retain five coordinate metal centers. 相似文献
17.
Sharaby CM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):326-334
Novel hexachlorocyclodiphosph(V)azane of sulfaguanidine, H(4)L, l,3-[N'-amidino-sulfanilamide]-2,2,2,4,4,4-hexachlorocyclodiphosph(V)azane was prepared and its coordination behaviour towards the transition metal ions Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO(2)(II) was studied. The structures of the isolated products are proposed based on elemental analyses, IR, UV-vis, (1)H NMR, mass spectra, reflectance, magnetic susceptibility measurements and thermogravimetric analysis (TGA). The hyperfine interactions in the isolated complex compounds were studied using 14.4keV gamma-ray from radioactive (57)Co (M?ssbauer spectroscopy). The data show that the ligand are coordinated to the metal ions via the sulfonamide O and deprotonated NH atoms in an octahedral manner. The H(4)L ligand forms complexes of the general formulae [(MX(z))(2)(H(2)L)H(2)O)(n)] and [(FeSO(4))(2) (H(4)L) (H(2)O)(4)], where X=NO(3) in case of UO(2)(II) and Cl in case of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II). The molar conductance data show that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied and different thermodynamic parameters were calculated using Coats-Redfern method. Most of the prepared complexes showed high bactericidal activity and some of the complexes show more activity compared with the ligand and standards. 相似文献
18.
The ligand has been
prepared from ω-chloroisonitrosoacetophenone and 1,4-phenylenediamine
in the presence of NaHCO3. The ligand have a C=O group
and an –NH–R group adjacent to the oxime group. The Ni(II), Cu(II)
and Co(II) complexes of the synthesized ligand were prepared and their structures
were identified using FTIR, UV-Vis spectral data, elemental analysis, thermal
analysis and magnetic moment measurements. The metal-ligand ratios were found
to be 3:2. The ligands were found to coordinate to the metal ions via the
oxime nitrogen, oxime oxygen, one of the carbonyl group and amide nitrogen
atoms. Thermal analyses data reveals that the water in the complexes was found
to be non-coordinated to the metal ions. In the trinuclear structures, the
metals have the tetrahedral environments. 相似文献
19.
New metal complexes of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with salicylidine-2-aminobenzimidazole (SABI) are
synthesized and their physicochemical properties are investigated using elemental and thermal analyses, IR, conductometric,
solid reflectance and magnetic susceptibility measurements. The base reacts with these metal ions to give 1:1 (Metal:SABI)
complexes; in cases of Fe(III), Co(II), Cu(II), Zn(II) and Cd(II) ions; and 1:2 (Metal:SABI) complexes; in case of Ni(II)
ion. The conductance data reveal that Fe(III) complex is 2:1 electrolyte, Co(II) is 1:2 electrolyte, Cu(II), Zn(II) and Cd(II)
complexes are 1:1 electrolytes while Ni(II) is non-electrolyte. IR spectra showed that the ligand is coordinated to the metal
ions in a terdentate mannar with O, N, N donor sites of the phenloic -OH, azomethine -N and benzimidazole -N3. Magnetic and
solid reflectance spectra are used to infer the coordinating capacity of the ligand and the geometrical structure of these
complexes. The thermal decomposition of the complexes is studied and indicates that not only the coordinated and/or crystallization
water is lost but also that the decomposition of the ligand from the complexes is necessary to interpret the successive mass
loss. Different thermodynamic activation parameters are also reported, using Coats-Redfern method.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
20.
Dithizone (Dz), a common extractive-photometric ligand for Co(II) and Ni(II), has been dissolved in the water-miscible solvent tetrahydrofurane (THF) so as to constitute a reagent for both metals in aqueous phase without extraction. Complex formation was complete for both metals at pH 12.0 (adjusted by aqueous NH(3)) within 30 min, and the complexes were stable for at least 2 h. First-derivative spectra of the metal dithizonates (singly or as binary mixtures) were preferred to ordinary spectra, because working wavelength determination was more precise and spectral overlap was less. Two wavelengths at which the spectral overlap was minimum were selected as analytical wavelengths, i.e. 620 nm for Co and 740 nm for Ni, and the calibration curves drawn with zero-to-peak values as a function of concentration were linear for these wavelengths. Thus, the total (1)D values at 620 and 740 nm of the mixtures were used to determine Co and Ni concentrations. The relative standard deviation (R.S.D.) for the analysis of Co (3.0 mg l(-1)) individually was 3.5%, and for its admixture with Ni (3.5 mg l(-1)) was 2.5%. The R.S.D. for the analysis of Ni (5.9 mg l(-1)) individually and for its admixture with Co (1.8 mg l(-1)) were 5.5 and 5.8%, respectively. The linear range in (1)D evaluation was between 5.0x10(-6) and 1.0x10(-4) M for Co and 2.0x10(-5)-2.0x10(-4) M for Ni. Interference analysis was performed for individual metal (Co or Ni) determinations. Finally, the method has been applied to a Ni-Cr-based dental alloy (Wiron 99) successfully. 相似文献