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1.
Zinc(II) complexes of alpha-amino acids and their derivatives with a Zn(N2O2) coordination mode were found to have in vitro insulinomimetic activity as estimated with the inhibition of free fatty acid release in isolated rat adipocytes treated with epinephrine. It was revealed that the insulinomimetic activities of zinc(II) complexes with over-all stability constants (log beta) less than 10.5 are higher than those of ZnSO4 and VOSO4. The high blood glucose level of KK-Ay mice with type 2 diabetes mellitus was lowered by daily intraperitoneal injections of a zinc(II) complex, cis-[Zn(L-Thr)2(H2O)2], for 14 d. The improvement of diabetes mellitus was confirmed with the oral glucose tolerance test.  相似文献   

2.
Yang W  Schmider H  Wu Q  Zhang YS  Wang S 《Inorganic chemistry》2000,39(11):2397-2404
Three novel Zn(II) complexes containing either 2,2',2"-tripyridylamine (2,2',2"-tpa) or 2,2',3"-tripyridylamine (2,2',3"-tpa) have been synthesized and structurally characterized. Compound 1, Zn(2,2',2"-tpa)Cl2, has a tetrahedral geometry while compounds 2, Zn(2,2',2"-tpa)2(O2CCF3)2, and 3, Zn(2,2',3"-tpa)4(O2CCF3)2, have an octahedral geometry. The 2,2',2"-tpa ligand in 1 and 2 functions as a bidentate ligand, chelating to the zinc center, while the 2,2",3"-tpa ligand in 3 functions as a terminal ligand, binding to the zinc center through the 3-pyridyl nitrogen atom. All three compounds emit a blue color in solution and in the solid state. The emission maxima for the three compounds in solution are at lambda = 422, 426, and 432 nm, respectively. The blue luminescence of the complexes is due to a pi *-->pi transition of the tpa ligand as established by an ab initio calculation on the free ligand 2,2',2"-tpa and complex 1. Compounds 1 and 2 are fluxional in solution owing to an exchange process between the coordinate and noncoordinate 2-pyridyl rings of the 2,2',2"-tpa ligand. Compound 2 is also fluxional owing to a cis-trans isomerization process, as determined by variable-temperature 1H NMR spectroscopic analysis.  相似文献   

3.
《Analytical letters》2012,45(11):577-586
Abstract

Thermodynamic parameters have been determined by poten-tiometric techniques for complex ions formed by N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine TKED, with nickel (II), copper(II), and zinc(II) ions. The formation constants, enthalpy, and free energy data for the complexes exhibited values qualitatively consistent with predicted ligand field stabilization trends for these cations. The general expected stability of the complexes in the order Ni(II) < Cu(II) > Zn(II) is observed.  相似文献   

4.
Zn(II) complexes are expected to be useful in the treatment of diabetes mellitus because of the hypoglycemic effect produced by its insulin-mimetic activity. Previous reports indicated that Zn(II) complexes with coordinating sulfur exhibit higher insulin-mimetic activity. In this study, we investigated the pharmacological and pharmacokinetic differences between Zn(O(4)) and Zn(S(2)O(2)) coordination modes of tropolonato-Zn(II) complexes with insulin-mimetic activity. Among the tropolonato-Zn(II) complexes with various coordination modes, di(2-mercaptotropolonato)zinc(II) (ZT2) with the Zn(S(2)O(2)) coordination mode was found to exhibit the highest in vitro insulin-mimetic activity with respect to inhibition of free fatty acid (FFA) release and enhancement of glucose uptake in isolated rat adipocytes treated with adrenaline. On comparing investigations of the antidiabetic effect in vivo, ZT2 was found to exhibit potent hypoglycemic activity and improve insulin resistance in type 2 diabetic KKA(y) mice at a low orally administered daily dose. Di(tropolonato)zinc(II) (ZT1), which has the Zn(O(4)) coordination mode, had a lesser effect at the same dose. In a pharmacokinetic analysis based on the (65)Zn tracer method, ZT2 was found to be absorbed at a significantly slower rate with a longer half-life than was ZT1. These results suggest that the potent hypoglycemic activity of ZT2 might be attributed to its long half-life.  相似文献   

5.
Reacting the heterocycle 5-thioxo-1,4-dihydro-4-ethyl-3-methyl-1,2,4-triazole (thioxotriazoline) with sodium tetrahydroborate in the molar ratio of approximately 2:1 at 130 degrees C provides the new ligand dihydrobis(thioxotriazolinyl)borato, [Bt(Et,Me)](-), as its sodium salt. The neutral complexes of this anionic ligand with zinc(II), bismuth(III), and nickel(II) have been synthesized and characterized by X-ray crystallography. In every complex, the ligand is coordinated to the metal in the S(2) mode, generating eight-membered chelate rings. The bismuth and nickel complexes exhibit two M.H-B interactions responsible for the dodecahedral and octahedral geometries, respectively. For the zinc complex, the trigonal-bipyramidal coordination is achieved with an apical Zn.H-B interaction. The crystal structures for the three complexes are described, and ab initio calculations on Bi(III), Ni(II), and Zn(II) compounds have been performed in order to assess the nature of the M.H-B interaction and its role for the definition of the molecular geometries.  相似文献   

6.
Neutral dimeric metallocyclic complexes of type [M(2)(L(1))(2)B(n)] (where M = cobalt(II), nickel(II) and zinc(II), L(1) is the doubly deprotonated form of a 1,3-aryl linked bis-beta-diketone ligand of type 1,3-bis(RC(O)CH(2)C(O))C(6)H(4) (R=Me, n-Pr, t-Bu) and B is pyridine (Py) or 4-ethylpyridine (EtPy)) have been synthesised, adding to similar complexes already reported for copper(II). New lipophilic ligand derivatives with R = octyl or nonyl were also prepared for use in solvent extraction experiments. Structural, electrochemical and solvent extraction investigations of selected metal complex systems from the above series are reported, with the X-ray structures of [Co(2)(L(1))(2)(Py)(4)] x 2.25CHCl(3) x 0.5H(2)O (R=Pr), [Co(2)(L(1))(2)(EtPy)(4)] (R=t-Bu), [Ni(2)(L(1))(2)(EtPy)(4)] (R=t-Bu), [Zn(2)(L(1))(2)(EtPy)(2)] (R=Me) and [Zn(2)(L(1))(2)(EtPy)(4)] (R=t-Bu) being presented. The electrochemistry of H(2)L(1) (R=t-Bu) and of [Fe(2)(L(1))(3)], [Co(2)(L(1))(2)(Py)(4)], [Ni(2)(L(1))(2)(Py)(4)], [Cu(2)(L(1))(2)] and [Zn(2)(L(1))(2)(Py)(2)] has been examined. Oxidative processes for the complexes are dominantly irreversible, but several examples of quasireversible behaviour were observed and support the assignment of an anodic process, seen between +1.0 and +1.6 V, as a metal-centred oxidation. The reduction processes for the respective metal complexes are not simple, and irreversible in most cases. Solvent extraction studies (water/chloroform) involving variable concentrations of metal, bis-beta-diketone and heterocyclic base have been performed for cobalt(II) and zinc(II) using a radiotracer technique to probe the stoichiometries of the extracted species in each case. Synergism was observed when 4-ethylpyridine was added to the bis-beta-diketone ligand in the chloroform phase. Competitive extraction studies show a clear uptake preference for copper(II) over cobalt(II), nickel(II), zinc(II) and cadmium(II).  相似文献   

7.
Zinc complexes derived from benzoic acids containing electron-withdrawing substituents have been synthesized from Zn(II)(bis-trimethylsilyl amide)(2) and the corresponding carboxylic acid (2,6-X(2)C(6)H(3)COOH, where X = F, Cl, or OMe) in THF and structurally characterized via X-ray crystallography. The 2,6-difluorobenzoate complex crystallizes from THF or CH(3)CN as a seven membered zinc aggregate, where the metal atoms are interconnected by a combination of 10 mu-benzoates and mu(4)-oxo ligands, that is, [(2,6-difluorobenzoate)(10)O(2)Zn(7)](solvent)(2), solvent = THF (1) and CH(3)CN (1a). On the other hand, the 2,6-dichlorobenzoate zinc derivative crystallizes from THF as a dimer, [(2,6-dichlorobenzoate)(4)Zn(2)](THF)(3) (2), where the two zinc centers are bridged by three benzoate ligand. One of the zinc centers possesses a tetrahedral ligand environment where the fourth ligand is a unidentate benzoate, and the other zinc center has an octahedral arrangement of ligands which is accomplished by the additional binding of three THF molecules. Upon dissolution of complex 1 or 2 in the strongly binding pyridine solvent, disruption of these zinc carboxylates occurs with concomitant formation of mononuclear zinc bis-benzoates with three pyridine ligands in the metal coordination sphere. Complexes 1 and 2 were found to be effective catalysts for the copolymerization of cyclohexene oxide and carbon dioxide to afford polycarbonates devoid of polyether linkages, that is, completely alternating copolymers. Although these catalysts or catalyst precursors in the presence of CO(2)/propylene oxide afforded mostly propylene carbonate, they did serve as efficient catalysts for the terpolymerization of carbon dioxide/cyclohexene oxide/propylene oxide. The reactivities of these zinc carboxylates were very similar to those previously reported analogous complexes which have not been structurally characterized. Hence, it is suggested here that all of these zinc carboxylates provide similar catalytic sites for CO(2)/epoxide coupling processes.  相似文献   

8.
In this paper we describe the electrochemical synthesis and characterization of new neutral manganese, iron, cobalt, nickel, copper, zinc, cadmium and lead complexes with the ligand bis(4-N-methylthiosemicarbazone)-2,6-diacetylpyridine, H4DAPTsz-Me. X-Ray structures of [Mn(H2DAPTsz-Me)(EtOH)2] 1, [Pb(H2DAPTsz-Me)] 3 and [Zn(H2DAPTsz-Me)]2.EtOH.2H2O 4, were also determined. In these complexes the ligand behaves as bis-deprotonated and SNNNS pentadentate. In the manganese complex the metal is heptacoordinated, in a distorted pentagonal-bipyramidal environment, with the N3S2 donor set of the ligand in the pentagonal girdle and two solvent molecules occupying the axial positions. In the lead complex 3 the metal is pentacoordinated, bound exclusively to the five donor atoms of the ligand, as a consequence of the existence of "inert pair effect". The bishelical zinc complex 4 shows each zinc atom with different coordination geometry, one octahedrally six-coordinate while the other is distorted tetrahedrally four-coordinate.  相似文献   

9.
Yokota S  Tachi Y  Itoh S 《Inorganic chemistry》2002,41(6):1342-1344
Copper(II) and zinc(II) complexes supported by a popular beta-diketiminate ligand (1(-), 2-mesitylamino-4-mesitylimino-2-pentene), [CuII(1)(AcO)] and [[ZnII(1)]2(mu-MeO)(mu-AcO)], have been demonstrated to undergo an oxidative degradation to give a ketone diimine derivative (2) under aerobic conditions. The crystal structures of the mononuclear copper(II) and dinuclear zinc(II) complexes of the beta-diketiminate ligand as well as the copper(II) complex of the modified ligand have been determined by X-ray crystallographic analysis. Mechanism for the oxidative degradation reaction of the beta-diketiminate ligand is also discussed.  相似文献   

10.
The electrode reaction Zn(II)/Zn(Hg) in complex chloride, bromide, and iodide solutions with DMSO as solvent and ammonium perchlorate as supporting electrolyte has been studied at the equilibrium potential by the faradaic impedance method and a square-wave method. Furthermore, double-layer data have been determined by electrocapillary measurements. The results indicate that the zinc chloride and bromide complexes do not contribute noticeably to the exchange current density, while in the iodide system both the solvated zinc ion and the first complex take part in the charge transfer. From the dissimilar results valid for water and DMSO solutions the conclusion is made that probably ligand bridging at the amalgam by the halide ions is operative in water solutions, whereas in DMSO the larger solvent molecules adsorbed can form a steric hindrance to ligand bridging by chloride or bromide ions.  相似文献   

11.
A series of mononuclear iron(II) and zinc(II) complexes of the new chiral Py(ProMe)2 ligand (Py(ProMe)2 = 2,6-bis[[(S)-2-(methyloxycarbonyl)-1-pyrrolidinyl]methyl]pyridine) have been prepared. The molecular geometry in the solid state (X-ray crystal structures) of the complexes [FeCl2(Py(ProMe)2)] (1), [ZnCl2(Py(ProMe)2)] (2), [Fe(OTf)2(Py(ProMe)2)] (3), [Fe(Py(ProMe)2)(OH2)2](OTf)2 (4), and [Zn(OTf)(Py(ProMe)2)](OTf) (5) are reported. They all show a meridional NN'N coordination of the Py(ProMe)2 ligand. The bis-chloride derivatives 1 and 2 represent neutral isostructural five-coordinated complexes with a distorted geometry around the metal center. Unusual seven-coordinate iron(II) complexes 3 and 4 having a pentagonal bipyramidal geometry were obtained using weakly coordinating triflate anions. The reaction of Zn(OTf)2 with the Py(ProMe)2 ligand afforded complex 5 with a distorted octahedral geometry around the zinc center. All complexes were formed as single diastereoisomers. In the case of complexes 3-5, the oxygen atoms of both carbonyl groups of the ligand are also coordinated to the metal. The stereochemistry of the coordinated tertiary amine donors in complexes 3-5 is of opposite configuration as in complexes 1 and 2 as a result of the planar penta-coordination of the ligand Py(ProMe)2. Complexes 1, 2, and 5 have an overall -configuration at their metal center, while the Fe(II) ion in complexes 3 and 4 has the opposite delta-configuration (crystal structures and CD measurements). The magnetic moments of iron complexes 1, 3, and 4 correspond to that of high-spin d6 Fe(II) complexes. The solution structures of complexes 1-5 were characterized by means of UV-vis, IR, conductivity, and CD measurements and their electrochemical behavior. These studies showed that the coordination environment of 1 and 2 observed in the solid state is maintained in solution. In coordinating solvents, the triflate anion (3, 5) or water (4) co-ligands of complexes 3-5 are replaced by solvent molecules with retention of the original pentagonal bipyramidal and octahedral geometry, respectively.  相似文献   

12.
The synthesis of the novel tripodal ligand [N(CH2CH2CH2OH)(CH2CH2SH)2] H3-4 is reported. The aliphatic tetradentate ligand is equipped with an unsymmetrical NOS2 donor set. It reacts with Ni(OAc)2 x 4H2O or Zn(BF4)2 x xH2O to give the complexes [Ni(H-4)]2 5 and [Zn(H-4)]4 6, respectively. The molecular structures of 5 and 6 have been determined by X-ray diffraction. In both cases multinuclear, mu-thiolato-bridged complexes, wherein the ligand coordinates with only three (NS2) of the four donor groups, had formed. The dinuclear complex 5 adopts a butterfly geometry and contains nickel(II) ions in a square-planar NS3 coordination environment. Cyclic voltammetry experiments indicate that the nickel centers in 5 are electron-rich but not overly sensitive toward oxidation. Complex 6 is tetranuclear and the four thiolato-bridged metal centers form a ring. It shows a distorted tetrahedral coordination geometry for the zinc(II) ions in an NS3 coordination sphere. In both complexes the hydroxyl functionalized ligand arm of the tripodal ligand remains uncoordinated.  相似文献   

13.
The Schiff base ligand, N,N'-bis-(2-furancarboxaldimine)-3,3'-diaminobenzidene (L) obtained by condensation of 2-furaldehyde and 3,3'-diaminobenzidene, was used to synthesize the mononuclear complexes of the type, [M(L)](NO3)2 [M=Co(II), Ni(II), Cu(II) and Zn(II)]. The newly synthesized ligand, (L) and its complexes have been characterized on the basis of the results of the elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz, FT-IR, 1H and 13C NMR, mass, UV-vis and EPR. EPR, UV-vis and magnetic moment data revealed a square planar geometry for the complexes with distortion in Cu(II) complex and conductivity data show a 1:2 electrolytic nature of the complexes. Absorption and fluorescence spectroscopic studies support that Schiff base ligand, L and its Cu(II) and Zn(II) complex exhibit significant binding to calf thymus DNA. The highest binding affinity in case of L may be due to the more open structure as compared to the metal coordinated complexes.  相似文献   

14.
Several complexes of 2-(indazol-1-yl)-2-thiazoline (TnInA) with the divalent ions Co and Zn have been synthesized by the direct combination of the ligand and the metal chloride or nitrate hydrated salts in ethanol. These complexes have been characterized by a variety of physical–chemical techniques. Moreover, the structures of [CoCl2(TnInA)2] · C2H6O (1) and [(M)(TnInA)2(H2O)2](NO3)2 (M = Co, 3; Zn, 4) were determined by single-crystal X-ray diffraction. In all the complexes, the ligand TnInA bonds to the metal ion through the indazole and thiazoline nitrogen atoms. In complex 1 the environment around the cobalt ion may be described as a distorted octahedron with two TnInA ligands and two chlorine ligands. Compounds 3 and 4 are isostructural with a distorted octahedral geometry around the metal center, being linked to two water molecules and two TnInA ligands. However, in complex [ZnCl2(TnInA)] (2) the zinc atom is four-coordinated with a probable tetrahedral environment with two chloro ligands and one TnInA ligand bonded to the metal ion.  相似文献   

15.
Hqpzc has been synthesized by a highly efficient procedure using the ionic liquid TBAB as an environmentally benign reaction medium. [Cu(qpzc)(OAc)]·H2O (1) and [Zn(qpzc)(OAc)(H2O)] (2), complexes of the deprotonated ligand, qpzc¯ [qpzc¯ = N-(quinolin-8-yl)pyrazine-2-carboxamide], have been synthesized and characterized by elemental analyses, spectroscopic methods, and X-ray crystallography. The coordination geometry around the metal ions in both complexes is distorted square pyramidal. The mono-anionic qpzc¯ is a tridentate unsymmetrical ligand furnishing an N3 set, occupying three of the four basal positions. Acetate is a bidentate ligand in 1 and unidentate in 2. The apical position in 2 is occupied by water. Quite strong O-H…O hydrogen bonds create columns of complexes [rod group p21(11)] in the copper complex, but in conjunction with π-π interactions, a 3D edifice in the zinc complex. The electrochemical behavior of the ligand and its copper and zinc complexes shows that the quinoline ring reduces at more positive potentials in these complexes relative to the free ligand. The in vitro antibacterial activities of these complexes were tested against Escherichia Coli and Staphylococcus Aureus.  相似文献   

16.
In vitro insulinomimetic activities of Zn(II) complexes with three natural products, betaine, L-lactic acid, and D-(-)-quinic acid (qui), were found in rat adipocytes treated with epinephrine in terms of the inhibition of free fatty acid release. Based on the results, the blood glucose lowering effect in KK-A(y) mice with type 2 diabetes mellitus was observed by daily i.p. injections of a monomeric zinc(II) complex, Zn(qui)(2), for 13 d.  相似文献   

17.
To investigate the different phosphorescent promoting effects of organic emitters by various metal centers, a new ligand, 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyrimidine (pmbp), and its Zn(II), Hg(II), and Pt(II) complexes, [Zn(pmbp)(2)](ClO(4))(2)(1), Pt(pmbp)Ph(2)(2), Zn(pmbp)Cl(2)(3), and Hg(pmbp)Cl(2)(4) were synthesized. Their structures were determined by single crystal X-ray diffraction. The zinc complexes 1 and 3 exhibit blue luminescence in the solid state at ambient temperature, but the mercury complex 4 is not luminescent. At 77 K, both pmbp and complex have blue emissions in MeOH solutions, which were demonstrated to be phosphorescence by their long decay lifetime (micros). By comparing the luminescent properties of the free ligand and the complex, we concluded that the phosphorescence of originates from ligand centered pi --> pi* transitions. Complex 2 exhibits orange luminescence both in CH(2)Cl(2) solution at 77 K and in the solid state at ambient temperature, which was assigned to metal-to-ligand [d(M) --> pi*(pmbp)] charge transfer (MLCT). The different origin of luminescence is responsible for the different luminescent color of the Zn(II) and Pt(II) complexes.  相似文献   

18.
Four mononuclear copper(II) and zinc(II) complexes were synthesized by the reaction of copper and zinc salts with 3,4-dichlorophenylactic acid, 2-bromophenylactic acid, biphenylacetic acid (O-donor ligand) and bipyridine (N-donor ligands) having the general formulae [(L)2Cu(bp)(H2O)] ( 1 ), [(BpA)2Cu(bp)] ( 2 ), [(L)2Zn(bp)(H2O)] ( 3 ) and [(L*)2Zn(bp)] ( 4 ) (L = 3,4-dichlorophenylacetate, L* = 2-bromophenylacetate bp = bipyridine, and BpA = biphenylacetate). Structures of all compounds were characterized through FT-IR spectroscopy and X-ray diffraction analysis. FT-IR spectra of all complexes confirmed the binding mode of Cu-O and Zn-O. XRD data revealed that complexes 1 – 3 exhibited distorted octahedral arrangement, whereas complex 4 has a distorted tetrahedral environment. Micellization behavior was examined with anionic surfactant (SDS) by conductance measurement as well as absorption spectral analysis. DNA binding study was assessed through viscosity measurement and UV/Vis spectrophotometry. DPPH free radical scavenging assay was measured by UV/Vis spectrophotometry. The results showed nice biological potential of all the complexes.  相似文献   

19.
Summary Mono- and binuclear zinc(II) complexes, Zn(HL)Cl and Zn2 (L-2H), containing multidentate acyldihydrazone ligands (H2L) have been synthesized and characterized by elemental analysis, i.r. and electronic spectral data. The reaction medium, zinc(II) salt and ligand geometry influence the composition and stereochemistry of the complexes.  相似文献   

20.
A ligand 1,3-bis(1-benzylbenzimidazol-2-yl)-2-oxopropane (Bobb) and the zinc(II) complex, [Zn(Bobb)2](picrate)2 · 2DMF, were synthesized and characterized by elemental analyses, electrical conductivities, IR, and UV. The crystal structures of the ligand and the zinc complex have been determined by single crystal X-ray diffraction. The ligand displays a V-shaped configuration and the Zn(II) cation is six-coordinate by four nitrogens and two oxygens from Bobb. The N4O2 donor set is a distorted octahedron.  相似文献   

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