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1.
The stability constants for the Tc(IV) and V(IV) complexation with the polyamino polycarboxylate ligands IDA, NTA, HEDTA and DTPA were determined using liquid–liquid extraction techniques. These stability constants were then used to evaluate the validity of using V(IV) as a chemical analogue for Tc(IV). Results suggest that Tc(IV), as TcOOH+, will form β 1?11 complexes with the selected ligands, while V(IV), as VO2+, will form β 101 complexes. The values for these determined stability constants are (in log10 unit) 10.9 ± 0.1, 11.4 ± 0.1, 14.9 ± 0.1, and 20.1 ± 0.1 for Tc(IV) in 0.5 mol·L?1 NaCl at 25 °C, for IDA, NTA, HEDTA and DTPA, respectively, they are 9.3 ± 0.1, 11.6 ± 0.2, 15.8 ± 0.1, and 20.8 ± 0.1 for V(IV) in 0.5 mol·L?1 NaCl at 25 °C, for the same suite of ligands. The incorporation of a hydroxide into the metal ligand complexes formed by Tc(IV) is proposed as the largest factor differentiating the apparent stability constants of Tc(IV) and V(IV). This work shows that V(IV) is a poor analog for Tc(IV); however, despite the differences in complexation mechanism between V(IV) and Tc(IV), V(IV) still appears to have some use for predicting Tc(IV) complexation behavior.  相似文献   

2.
Complex formation equilibria of aluminum(III), gadolinium(III), and yttrium(III) ions with the fluoroquinolone antibacterials moxifloxacin, ofloxacin, fleroxacin, lomefloxacin, levofloxacin, and ciprofloxacin were studied in aqueous solution by potentiometric and spectroscopic methods. The identity and stability of metal–fluoroquinolone complexes were determined by analyzing potentiometric titration curves (310 K, μ = 0.15 M NaCl, pH range = 2–11, CL/CM = 1?:?1 to 3?:?1, CM = 1.0 mM) with the aid of Hyperquad2006 program. The main species formed in the system may be formulated as MpHqLr (p = 1, q = ?2 to 2, r = 1–3, L = fluoroquinolone anion, logarithm of overall stability constant, log βp,q,r = in the range ca. ?10 to 45). The stability of complexes is mostly influenced by metal ion properties (ionization potential, ionic radius) indicating partial ionic character of the coordination bond. The complexes were also characterized by spectroscopic measurements: spectrofluorimetry, 1H-NMR, and ESI-MS. Fluorimetric data were evaluated with the aid of HypSpec2014 and indicated the formation of MLr (r = 1–3) complexes with cumulative conditional stability constants significantly lower than the thermodynamic ones. NMR and MS data corroborate potentiometrically determined speciation. Calculated plasma mobilizing capacity of the ligands generally follows the order levofloxacin > moxifloxacin > ciprofloxacin at concentration levels of the ligands higher or equal to ca. 10?4 M.  相似文献   

3.
The formation of binary and ternary complexes of the divalent transition metal ions CuII, NiII, ZnII, and CoII with some triazoles [1,2,4-triazole (TRZ), 3-mercapto-1,2,4-triazole, and 3-amino-1,2,4-triazole], and the biologically important aliphatic dicarboxylic acids adipic, succinic, malic, malonic, maleic, tartaric, and oxalic acid, was investigated in aqueous solutions using the potentiometric technique at 25 °C and I = 0.10 mol·dm?3 NaNO3. The formation of 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes was inferred from the corresponding titration curves. The formation of ternary complexes occurs in a stepwise manner with the carboxylic acids acting as primary ligands. The ionization constants (pK a) of the investigated ligands were redetermined and used for determining the stability constants of the binary and ternary complexes formed in solution. The order of stability of the ternary complexes was investigated in terms of the nature of the triazole, carboxylic acid and metal ion used. The ?log10 K values, percent relative stabilization, and log10 X for the ternary complexes have been evaluated and discussed. The concentration distributions of the various species formed in solution were evaluated. The ionization constants of TRZ and malic acid and stability constants of their binary and ternary complexes with CuII, NiII, and CoII metal ions were studied at four different temperatures (15, 25, 35, and 45 °C) and the corresponding thermodynamic parameters have been evaluated and discussed. The complexation behavior of ternary complexes was ascertained using conductivity measurements. In addition, the formation of ternary complexes in solution has been confirmed by using UV–visible spectrophotometry.  相似文献   

4.
One isomer, LC of the isomeric Me8[14]anes, LA, LB and LC; on reaction with Ni(NCS)2 produces a six coordinate octahedral diisothiocyanato complex, [NiLC(NCS)2]. This complex undergoes axial substitution reactions with the small ligands to yield corresponding monosubstituted derivatives having general formula [NiLC(NCS)X] whereas X = Cl, Br, I, NO2 or NO3. The complexes have been characterized on the basis of analytical, spectroscopic, magnetic and conductance data. The structure of [NiLC(NCS)2] (triclinic, space group P?1, α = 8.0421(17) Å, β = 8.9085(18) Å, χ = 9.687(2) Å, α = 67.561(3) Å, β = 82,896(4) Å, ζ = 598.7(2) Å3, = 2, Dc = 1.352 mg/m3, μ(Mo ) = 1.003 mm?1) was confirmed by X-ray crystallography.  相似文献   

5.
The protonation constants and solubilities of three complexons [ethylenediamine-N,N′-disuccinic acid (EDDS), ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) and 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA)] are reported in aqueous solutions of NaCl with different ionic strength values (0 ≤ I ≤ 4.8 mol·L?1) and, in the case of CDTA, in (CH3)4NCl (0.1 ≤ I ≤ 2.7 mol·L?1). The dependence on ionic strength of the protonation constants of these three complexons and four other complexons that were previously reported (NTA, EDTA, DTPA and TTHA), is analyzed in NaCl solution; the ionic strength influences quite strongly the protonation constants (as an example for CDTA, log10 K 1 = 10.54 and 9.25 at I = 0.1 and 1 mol·L?1, respectively), while the effect of (CH3)4NCl concentration is lower. Based on the total solubility S T and the protonation constant data at different salt concentrations, the solubility of the neutral species S 0 and the solubility products K S0 are obtained. The Setschenow coefficients k m and the solubility values S 0 0 in pure water are also reported (S 0 0  = 0.55, 0.21 and 0.75 mmol·kg?1 for EDDS, EGTA and CDTA, respectively). The dependence of the protonation constants on ionic strength is also interpreted in terms of ion pair formation, and the formation constants of Na+ species are reported.  相似文献   

6.
Seven-coordinate Fe(III) complexes [Fe(dapsox)(H2O)2]+, where [dapsox = 2,6-diacetylpyridine-bis(semioxamazide)] is an equatorial pentadentate ligand with five donor atoms (2O and 3N), were studied with regard to their acid–base properties and complex formation equilibria. Stability constants of the complexes and the pK a values of the ligands were measured by potentiometric titration. The interaction of [Fe(dapsox)(H2O)2]+ with the DNA constituents, imidazole and methylamine·HCl were investigated at 25 °C and ionic strength 0.1 mol·dm?3 NaNO3. The hydrolysis constants of the [Fe(dapsox)(H2O)2]+ cation (pK a1 = 5.94 and pK a2 = 9.04), the induced ionization of the amide bond and the formation constants of the complexes formed in solution were calculated using the nonlinear least-squares program MINIQUAD-75. The stoichiometry and stability constants for the complexes formed are reported. The results show the formation of 1:1 and 1:2 complexes with DNA constituents supporting the hepta-coordination mode of Fe(III). The concentration distributions of the various complex species were evaluated as a function of pH. The thermodynamic parameters ΔH° and ΔS° calculated from the temperature dependence of the equilibrium constants were investigated for interaction of [Fe(dapsox)(H2O)2] with uridine.  相似文献   

7.
In this study the binary and ternary complexes of copper(II) with substituted 1,10-phenanthrolines [s-phen: 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dmphen) and 5-nitro-1,10-phenanthroline (nphen)] and l-amino acids [aa: l-phenylalanine (phe), l-tyrosine (tyr) and l-tryptophan (trp)] have been investigated using potentiometric methods in 0.1 mol·L?1 KCl aqueous ionic media at 298.2 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. It was inferred that the aromatic 1,10-phenanthrolines act as a primary ligand in the ternary complexes, while the oxygen and nitrogen donor-containing amino acids are secondary ligands. The observed values of Δlog10 K indicate that the ternary complexes are more stable than the binary ones, suggesting no interaction takes place between the ligands in the ternary complexes. The magnitudes of the measured stability constants of all of the ternary complexes are in the order [Cu(s-phen)(trp)]+ > [Cu(s-phen)(tyr)]+ > [Cu(s-phen)(phe)]+, which is identical to the sequence found for the binary complexes of Cu(II) with the amino acids. When the substituted 1,10-phenanthroline is changed, the stability constants of the ternary complexes decrease in the following order: [Cu(dmphen)(aa)]+ > [Cu(phen)(aa)]+ > [Cu(nphen)(aa)]+.  相似文献   

8.
Substitution reactions of the dinuclear Pt(II) complexes, [{Pt(en)Cl}2(μ-pz)]2+ (1), [{Pt(dach)Cl}2(μ-pz)]2+ (2) and [{Pt(dach)Cl}2(μ-4,4?-bipy)]2+ (3), and corresponding aqua analogs with selected biologically important ligands, viz. 1,2,4-triazole, L-histidine (L-His) and guanosine-5?-monophosphate (5?-GMP) were studied under pseudo-first-order conditions as a function of concentration and temperature using UV–vis spectrophotometry. The reactions of the chloride complexes were followed in aqueous 25 mmol L?1 Hepes buffer in the presence of 40 mmol L?1 NaCl at pH 7.2, whereas the reactions of the aqua complexes were studied at pH 2.5. Two consecutive reaction steps, which both depend on the nucleophile concentration, were observed in all cases. The second-order rate constants for both reaction steps indicate a decrease in the order 1 > 2 > 3 for all complexes. Also, the pKa values of all three aqua complexes were determined. The order of the reactivity of the studied ligands is 1,2,4-triazole > L-His > 5?-GMP. 1H NMR spectroscopy and HPLC were used to follow the substitution of chloride in the dichloride 1, 2, and 3 complexes by guanosine-5?-monophosphate (5?-GMP). This study shows that the inert and bridging ligands have an important influence on the reactivity of the studied complexes.  相似文献   

9.
Formation constants of mixed ligand complexes of Cu2+, Zn2+, Ni2+, Co2+, and Mn2+,with cyadine-5′-monophosphoric acid (CMP) and various primary ligands such as 1,10-phenanthroline(phen), glycylglycine(glygly) and salicylic acid (sal) have been determined in aqueous solution at 35°C and 0.1 M (KNO3) by potentiomeric measurements. The acid dissociation constants of all the above mentioned ligands together with their 1 : 1 binary metal complex formation constants were also measured at 35°C. In general all the 1 : 1 binary complexes follow the Irving-Williams order of stability. Further the binary metal complexes of primary ligands are more stable than their ternary complexes with CMP. For ternary complexes, Δ(log K) values seem to change from positive to highly negative as the coordinating atoms of the primary ligands were varied from N,N to N,O? to O?O?. The higher stability of ternary complexes involving phen is due to its Π-bonding interaction with the above metal ions and the relative decrease in the stability of other ternary systems is due to the coulombic repulsion of donor oxygen atoms of primary and secondary ligands. Thus for ternary complexes the stabilities follow a decreasing order of M-phen-CMP > M-glygly-CMP > M-sal-CMP.  相似文献   

10.
The complexation reactions of iron(III) with 2-pyridine carboxylic acia (picolinic acid) and 2,6-pyridine dicarboxylic acid (dipicolinic acid) in aqueous solutions have been studied by spectrophotometric and stopped flow techniques. Equilibrium constants were determined for the 1 : 1 complexes at temperatures between 25 and 80°C. The values obtained are: Picolinic Acid (HL): Fe3++ H2L+? FeHL3++H+(K1 = 2.8,ΔH = 2 kcal mole?1 at 25°C, μ = 2.67 M) Dipicolinic Acid (H2D): Fe3++H2D? FeD++2H+(K1K1A= 227 M, ΔH = 3.4 kcal mole?1 at 25°C,μ = 1.0 M). The rate constants for the formation of these complexes are also given. The results are used to evaluate the effects of these two acids upon the rate of dissolution of iron(III) from its oxides.  相似文献   

11.
12.
The stability constants of the binary ML2+ and ternary M(ATP)L2- complexes,where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+,have been determined by poten-tiometric pH titration in aqueous solution at I=0.1 mol/L (NaClO4),T=25℃.The stability of the ternary complexes characterized by corresponding to the equilibrium M(ATP)2-+ML2+=M(ATP)L2-+M2+ is higher than what would be expected on statistical grounds.The increase may be related to the stacking interaction between the aromatic ring of the ligands L and the purine moiety of ATP4- 1H NMR studies of Zn2+/ATP4-/L confirm the presence of stacking in the ternary complexes.It is concluded that the strength of the intramolecular stacking interaction is dependent on the structure of the aromatic ring of the ligand L and the formation of a metal ion bridge.Possible implications are discussed briefly.  相似文献   

13.
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   

14.
Redox reactions of Co(edta)? with Ru(NH3)5L2+ (L = 3- and 4-aminopyridine (AmPy)) were found to follow an outer-sphere electron transfer mechanism. The specific rate constants are (3.26 ± 0.03) × 102 and (3.07 ± 0.04) × 103 M?1S?1, for L = 3- and 4-AmPy, respectively, at μ, = 0.10 M LiClO4, pH = 8.0 (tris) and T = 25 °C. The rate constants of oxidations for a series of Ru(NH3)5L2+ complexes are higher than those of the corresponding Fe(CN)5L3- complexes by factors of 4 to 15 even after corrections for differences in reduction potentials and in charges of the complexes. Nonadiabaticity in the reactions of Fe(CN)5L3 complexes may account for the difference in the relative reactivities.  相似文献   

15.
The reaction of [(η5-C5Me5)M(μCl)Cl]2 with the ligand (LL) in the presence of sodium methoxide yielded compounds of general formula [(η5-C5Me5)M(LL)Cl] (1–10) (where M = Ir or Rh and LL = NO or OO chelate ligands). Azido complexes of formulation [(η5-C5Me5)M(LL)N3] (11–20) have been prepared by the reaction of [(η5-C5Me5)M(μN3)(X)]2 (X = Cl or N3) with the corresponding ligands or by the direct reaction of [(η5-C5Me5)M(LL)Cl] with NaN3. These azido complexes [(η5-C5Me5)M(LL)N3] undergo 1,3-dipolar cycloaddition reaction with substituted alkynes in CH2Cl2 and for the first time in ethanol at room temperature to yield iridium (III) and rhodium (III) triazoles (21–28). The compounds were characterized on the basis of spectroscopic data, and the molecular structures of 2 and 26 have been established by single crystal X-ray diffraction.  相似文献   

16.
The reactions of three polypyridylamine ferrous complexes, [Fe(TPEN)]2+, [Fe(TPPN)]2+, and [Fe(TPTN)]2+, with nitric oxide (NO) (where TPEN = N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine, TPPN = N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,2-propylenediamine, and TPTN = N,N,N′,N′-tetrakis(2-pyridylmethyl)trimethylenediamine) were investigated. The first two complexes, which are spin-crossover systems, presented second-order rate constants for complex formation reactions (kf) of 8.4 × 103 and 9.3 × 103 M?1 s?1, respectively (pH 5.0, 25 °C, I = 0.1 M). In contrast, the [Fe(TPTN)]2+ complex, which is in low-spin ground state, did not show any detectable reaction with NO. kf values are lower than those of high-spin Fe(II) complexes, such as [Fe(EDTA)]2? (EDTA = ethylenediaminetetraacetate) and [Fe(H2O)]2+, but higher than low-spin Fe(II) complexes, such as [Fe(CN)5(H2O)]3? and [Fe(bipyridine)3]2+. The release of NO from the [Fe(TPEN)NO]2+ and [Fe(TPPN)NO]2+ complexes were also studied, showing the values 15.6 and 17.7 s?1, respectively, comparable to the high-spin aminocarboxylate analogs. A mechanism is proposed based on the spin-crossover behavior and the geometry of these complexes and is discussed in the context of previous publications.  相似文献   

17.
The stability constants and the associated thermodynamic parameters of formation for the 1:1 binary complexes of Am3+, Cm3+ and Eu3+ with N-(2-hydroxyethyl) ethylenediaminetriacetate (HEDTA) and their 1:1:1 ternary complexes with HEDTA + NTA (nitrilotriacate) were determined by distribution ratio measurements using solvent extraction in aqueous solutions of I=0.10?mol?L?1 (NaClO4) at temperatures of 0?C45?°C. Formation of these complexes is favored by both the enthalpy (exothermic) and the entropy (endothermic) terms. Luminescence lifetime measurements with Cm and Eu were used to study the coordination environment of these complexes over a range of concentrations and pH values. In the binary complexes M(HEDTA), HEDTA is a hexadentate ligand with three waters of hydration, while in the ternary complexes M(HEDTA)(NTA)3? we propose that the HEDTA retaines hexadentate coordination with NTA binding via three sites, depending on the pH of the solution, with the observation that the complex may contain a single water of hydration.  相似文献   

18.
Four new mononuclear triazido-cobalt(III) complexes [Co(L 1/2/4 )(N3)3] and [Co(L 3 )(N3)3]·CH3CN where L 1  = [(2-pyridyl)-2-ethyl]-(2-pyridylmethyl)-N-methylamine, L 2  = [(2-pyridyl)-2-ethyl]-[6-methyl-(2-pyridylmethyl)]-N-methylamine, L 3  = [(2-pyridyl)-2-ethyl]-[3,5-dimethyl-4-methoxy-(2-pyridylmethyl)]-N-methylamine, and L 4  = [(2-pyridyl)-2-ethyl]-[3,4-dimethoxy-(2-pyridylmethyl)]-N-methylamine, respectively, were synthesized and structurally characterized. The four complexes were characterized by elemental microanalyses, IR and UV–VIS spectroscopy and X-ray single crystal crystallography. The complexes display two strong IR bands over the frequency region 2,020–2,050 cm?1 assigned for the asymmetric stretching frequency, νa(N3) of the coordinated azides indicating facial geometry. The molecular structure determinations of the complexes were in complete agreement with fac-[Co(L)(N3)3] conformation in distorted octahedral Co(III) environment.  相似文献   

19.
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   

20.
The equilibrium of distribution of Yb(III) and Lu(III) between chloroform and the aqueous phase in the presence of cupferron (the ammonium salt of N-nitrosophenylhydroxylamine) were studied as apH function of the aqueous phase and the concentration of N-nitrosophenylhydroxylamine (HL). The stability constants for theLnL n 3–n ) complexes (n=1÷3) being formed in the aqueous phase were established, as well as the equilibrium constants of the extraction reaction $$Ln(H_2 O)_m^{3 + } + 3HL_{(O)} \mathop \rightleftharpoons \limits^{K_{ex} } LnL_{3(O)} + 3H^ + + mH_2 O(Ln^{3 + } = Yb,Lu),$$ two-phase stability constants for theLnL 3 complexes,pH 0.5 and the separation factor Lu(III) from Yb(III).  相似文献   

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