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1.
Equilibrium studies in aqueous solution are reported for dimethyltin(IV) complexes of the zwitterionic buffers “Good’s buffer”, such as Mes and Mops (L). Stoichiometry and stability constants for the complexes formed were determined at different temperature and ionic strength 0.1 M NaNO3. The results showed the best fit of the titration curves were obtained when complexes ML, MLH−1, MLH−2, and MLH−3 were expected beside the hydrolysis products of the dimethyltin(IV) cation. The thermodynamic parameters Δ, Δ and Δ calculated from the temperature dependence of the formation constant of the dimethyltin(IV)-Mes complex was investigated. The effect of dioxane as a solvent on the formation constants of dimethyltin(IV)-Mes complex was discussed. The concentration distribution of the various complex species was evaluated as a function of pH. The bonding sites of the dimethyltin(IV) complexes in solid state with Mes and Mops were characterized by means of elemental analyses and FTIR. The NMR (1H, 13C) spectra of the DMT-Mes complex exhibits the strongly distorted octahedron geometry around tin atom. Also, thermal analyses (TGA and DTA) were discussed. Thermodynamic parameters such as activation energy (Ea), pre-exponential factor (A), entropy of activation (ΔS) and free energy of activation (ΔG) have been calculated for each step, employing integral method Coats and Redfern. The reaction enthalpy (ΔH) is obtained from DTA data.  相似文献   

2.
Equilibrium studies in aqueous solution are reported for dibutyltin(IV) (DBT) complexes of the zwitterionic buffers “Good’s buffers” Mes and Mops. Stoichiometric and formation constants of the complexes formed were determined at different temperatures and ionic strength 0.1 mol·L?1 NaNO3. The results show that the best fit of the titration curves were obtained when the complexes ML, MLH?1, MLH?2 and MLH?3 were considered beside the hydrolysis product of the dibutyltin(IV) cation. The thermodynamic parameters ΔH o, ΔS o and ΔG o calculated from the temperature dependence of the formation constant of the dibutyltin(IV) complexes with 2-(N-morpholino)ethanesulfonic acid (Mes) and 3-(N-mor-pholino)-propanesulfonic acid (Mops) were investigated. The effect of dioxane as a solvent on the formation constants of DBT–Mes and DBT–Mops complexes decrease linearly with the increase of dioxane proportion in the medium. The concentration distribution of the various complexes species was evaluated as a function of pH.  相似文献   

3.
Summary. Equilibria studies in aqueous solution containing 25% dioxane (V/V) are reported for dimethyltin(IV) and trimethyltin(IV) (M) complexes with some imidazole derivatives (L). Stoichiometry and stability constants for the complexes formed were determined at 25°C and ionic strength 0.1M NaNO3. The results of the dimethyltin(IV) complexes showed the best fit of the titration curves when complexes ML, ML 2, ML 2H–1, and ML 2H–2 were expected beside the hydrolysis products of the dimethyltin(IV) cation, while the calculations of the trimethyltin(IV) complexes reported the presence of only the complexes ML, MLH–1, and the hydrolysis products of the trimethyltin(IV) cation. The concentration distribution of each species of the complexes in solution was evaluated. The stability of all complexes formed was investigated and discussed in terms of molecular structure of the ligand imidazole and the nature of the alkyltin cation. It is deduced that the stability of the complex formed increases as the basicity of the ligand imidazole is increased. On the other hand, the trimethyltin(IV) cation has a very low ability to form complexes compared to the dimethyltin(IV) cation.Received November 22, 2002; accepted (revised) March 3, 2003 Published online August 18, 2003  相似文献   

4.
The aqueous coordination behavior of two novel tripodal imine-phenol ligands, cis,cis-1,3,5-tris{(2-hydroxybenzilidene)aminomethyl}cyclohexane (TMACHSAL, L1) and cis,cis-1,3,5-tris{[(2-hydroxyphenyl)ethylidene]aminomethyl}cyclohexane (Me3- TMACHSAL, L2) with Al3+ and Ga3+ has been investigated at an ionic strength of 0.1 mol⋅dm−3 KCl and 25±1 °C by potentiometric and spectrophotometric methods. Both ligands formed various monomeric metal complex species MLH3, MLH2, MLH, ML and MLH−1 with Ga(III); and MLH3, ML and MLH−1 with Al(III). The Ga(III) complexes showed higher thermodynamic stability than the Al(III) complexes. Semi-empirical PM6 calculations along with TDDFT/B3LYP/3-21G calculations have been performed to complement the experimental measurements. The calculated structure of the metal complexes predicted a distorted octahedral geometry where favorable ring-flipping from the equatorial conformation in uncomplexed ligands to the axial conformation was observed upon chelation.  相似文献   

5.

Abstract  

The complexation of a tripodal amine-catechol ligand tris((2,3-dihydroxybenzylamino)ethyl)amine (TRENCAT, L) with group-13 metal ions, viz., Al(III), Ga(III), and In(III), were investigated by means of potentiometric titrations and spectrophotometric measurements in an aqueous medium of 0.1 M KCl at 25 ± 1 °C. The ligand shows the potential to form various monomeric complexes of the types MLH3, MLH2, MLH, and ML. At low pH, the ligand is coordinated through three more acidic ortho-catecholic O-atoms to give MLH3 species. With the rise in pH, the species MLH3 releases three protons in steps from the meta-catecholic O-atoms to form MLH2, MLH, and ML. The order of stability Ga(III) > Al(III) > In(III) for the species MLH3 and MLH2 is changed into Al(III) > Ga(III) > In(III) for the species MLH and ML. The coordination modes, binding ability, selectivity, and the change in stability order were explained with the help of experimental evidence, molecular modeling calculations, and available literature.  相似文献   

6.

Complex formation equilibria of divinyltin(IV) with amino acids, peptides, and dicarboxylic acids have been investigated. Stoichiometry and stability constants for the complexes formed were determined at 25°C and ionic strength 0.1 M NaNO3. The results showed the formation of ML, MLH, and ML2 (organotin : ligand : hydrogen) complexes with amino acids. Peptides form ML complexes and the corresponding deprotonated amide species MLH?1. In the latter species the binding with divinyltin(IV) occurs through the terminal amino group, carboxylate oxygen, and the amide nitrogen atoms (CO? 2, N? amide, NH2). The results showed the formation of ML and ML2 complexes with dicarboxylic acids. The concentration distribution of the complexes in solution was evaluated. The bonding sites of the divinyltin(IV) complex in solid state with oxalic acid was investigated by means of elemental analyses, FTIR, and mass spectra. Non-isothermal decomposition of the above complex has been studied and the result was statistically analyzed. The main steps were identified for the thermal decomposition reaction and each step proved to be a first order reaction. The kinetic parameters E a and A were calculated for each step in the reaction. The thermodynamic functions H, G, and S* were calculated for each step of the reaction.  相似文献   

7.
The protonation equilibria of 2-amino-N-(2-oxo-2-(2-(pyridin-2-yl)ethyl amino)ethyl)acetamide ([H2(556)–N]) and the complexation of this ligand with Cu(II) Ca(II), Zn(II) and Ni(II) have been studied by glass electrode potentiometry and UV–visible spectrophotometry. From pH ∼2.00–11.00, five models for Cu(II) with the following complexes; MLH, ML, MLH−1, MLH−2 and MLH−3 were generated and observed to describe the experimental data equally well as far as the statistical criteria were concerned. The MLH−2 complex predominates at physiological pH in all five models, while the MLH−1 complex species exists only at low concentration in two models. The coordination in the MLH−2 complex suggested the involvement of one amino, two deprotonated peptides and one pyridyl nitrogen atoms. Molecular mechanics (MM) calculations confirmed the MLH−2 complex as the most stable species. Speciation calculations, using a blood plasma model, predicted that the Cu(II)–[H2(556)–N] complex is able to mobilize Cu(II). Octanol/water partition of CuLH−2 showed that 30% of the complex went into the octanol phase, hence promoting percutaneous absorption of copper. The complex is a poor mimic of native copper–zinc superoxide dismutase.  相似文献   

8.
Abstract  The complexation of a tripodal amine-catechol ligand tris((2,3-dihydroxybenzylamino)ethyl)amine (TRENCAT, L) with group-13 metal ions, viz., Al(III), Ga(III), and In(III), were investigated by means of potentiometric titrations and spectrophotometric measurements in an aqueous medium of 0.1 M KCl at 25 ± 1 °C. The ligand shows the potential to form various monomeric complexes of the types MLH3, MLH2, MLH, and ML. At low pH, the ligand is coordinated through three more acidic ortho-catecholic O-atoms to give MLH3 species. With the rise in pH, the species MLH3 releases three protons in steps from the meta-catecholic O-atoms to form MLH2, MLH, and ML. The order of stability Ga(III) > Al(III) > In(III) for the species MLH3 and MLH2 is changed into Al(III) > Ga(III) > In(III) for the species MLH and ML. The coordination modes, binding ability, selectivity, and the change in stability order were explained with the help of experimental evidence, molecular modeling calculations, and available literature. Graphical Abstract     相似文献   

9.
The interaction of dimethyltin(IV) dichloride (DMT) with 1,4-piperazine (PIP) was investigated. The complex formation equilibria of the complexes formed in solution were investigated. The stoichiometry and stability constants of the complexes formed in solution phase were determined at different temperatures and in solutions of dioxane–water mixtures of different dielectric constants. The equilibrium constant for the displacement of piperazine coordinated to dimethyltin(IV) by inosine as a representative of DNA was calculated. (DMT)(PIP)·3H2O was synthesized and characterized by elemental analysis, spectral, and thermal techniques. The antitumor activity of the complex was screened.  相似文献   

10.
pK values of N,N-dihydroxyethylglycine (bicine) and N-[tris(hydroxymethyl)methyl]-glycine (tricine) have been determined by the Irving-Rossotti method in an aqueous medium at 25, 30, 35, 40, 45, and 50°C and at different ionic strengths (I = 0.1, 0.5, and 1.0). Plots between pKa(NH) and 1/T for various ionic strengths have been obtained and the values of slopes have been used to calculate the ΔH, ΔS, and ΔG for the dissociation reactions of bicine and tricine. The ΔH, ΔS, and ΔG values for bicine were found to be 10.6 ± 0.6 kcal mol?1, ?1.9 ± 1.8 e.u., and 11.1 ± 0.06 kcal mol?1, respectively, and for tricine 11.2 ± 0.6 kcal mol?1, 1.6 ± 1.6 e.u., and 10.7 ± 0.06 kcal mol?1, respectively. The pKa(NH) values decrease with rise in temperature but the influence of ionic strength is not significant.  相似文献   

11.
Abstract

Six diorganotin(IV) derivatives of α-aminoacids with general formulae [(CH3)2 SnAACl]2 and [(CH3CH2CH2CH2)2SnAACl]2, where AA = L-alaninate, L-phenylalaninate, and L-isoleucinate, have been synthesized by reacting dimethyltin(IV) dichloride (M) and dibutyltin(IV) dichloride (B) with L-alanine (A) or L-phenylalanine (PA) or L-isoleucine (I) using acetonitrile as the solvent and designated as MA, MPA, MI, BA, BPA, and BI. These complexes have been characterized by elemental analysis, infrared (IR), 1H NMR, 13C NMR, and 119Sn NMR spectroscopy. Thermal studies of all of the synthesized complexes were also carried out using thermogravimetric (TG) and differential scanning calorimetry (DSC) techniques. The thermal decomposition mechanisms were similar for MA, BA, MI, and BI and occurred in one step, while in compounds MPA and BPA, it occurred in two consecutive steps. The TG curves of MPA and BPA suggest the loss of the ligand (AA) in the first step, with probable formation of a tin oxide R2SnO as an intermediate, and in the second step, free tin is obtained, similar to MA, BA, MI, and BI, in accordance with the stoichiometry of the related derivatives. The diorganotin(IV) complexes have also been screened for their antibacterial activity against Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, and Pseudomonas aeruginosa. The minimum inhibitory concentration values of these complexes show enhanced activity.  相似文献   

12.
The three ligands 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis(methylenephosphonic acid) ( 1 ), 1,4,7,11-tetraazacyclotridecane-1,4,7,11-tetrakis(methylenephosphonic acid) ( 2 ), and 1,4,8,11-tetraazacyclotetradecane-1,4,8,1 1-tetrakis(methylenephosphonic acid) ( 3 ) have been synthesized by condensation of the corresponding macrocycles with formaldehyde and phosphorous acid. The protonation and stability constants with the earth-alkali ions have been determined at 25° and I = 0.1 M (Me4)N(NO3) by potentiometric titrations. Because of the high values of the first two protonation constants, 1H-NMR measurements were necessary to determine them. Titrations in different supporting electrolytes (NaNO3, KNO3, RbNO3, CsNO3, and Me4N(NO3)) show that their choice is of paramount importance, as the above ligands can form complexes with alkali-metal ions. The potentiometric results for the earth-alkali ions show that beside mononuclear complexes of different degrees of protonation ([MLHn], n = 0–4), also binuclear species are formed ([M2LHm], m = 0–2). It is interesting that 1 with the smallest macrocyclic ring has the greatest tendency to form binuclear complexes, which are so stable that they partially prevent the formation of the corresponding mononuclear species. For [ML], [MLH], [M2L], and [M2LH], the stability sequence is Mg2+ < Ca2+ > Sr2+ > Ba2+, whereas for [MLH2], [MLH3], and [MLH4], the stability steadily decreases from Mg2+ to Ba2+.  相似文献   

13.
The complex-formation equilibria of dimethyltin(IV) (DMT) with 4-hydroxymethyl imidazole (HMI) and 2,6-dihydroxymethyl pyridine (PDC) have been investigated. Stoichiometry and stability constants for the complexes formed were determined at different temperatures and 0.1?mol?L?1 NaNO3 ionic strength. The concentration distribution of the complexes in solution was evaluated as a function of pH. The effect of dioxane as a solvent on both protonation constants and formation constants of DMT complexes with HMI and PDC are discussed. The thermodynamic parameters ΔH° and ΔS° calculated from the temperature dependence of the equilibrium constants were investigated.  相似文献   

14.
The study was focused on the structure–activity relationship of some newly synthesized hexacoordinated dimethyltin(IV) complexes of fluorinated β‐diketone/β‐diketones and sterically congested heterocyclic β‐diketones. These complexes were screened for their antibacterial activity against a Gram‐negative bacterium (Pseudomonas aeruginosa) and Gram‐positive bacteria (Streptomyces griseus, Staphylococcus aureus, Bacillus subtilis) and the results were compared with those of a standard antibacterial drug. Some of the complexes were also screened for their antifungal activity against various fungi (Aspergillus niger, A. flavus, Trichoderma viride, Fusarium oxysporum) and were found to be active. These new hexacoordinated complexes of dimethyltin(IV) were generated by reactions of dimethyltin(IV) dichloride and sodium salts of fluorinated β‐diketone/β‐diketones and sterically congested heterocyclic β‐diketones in 1:1:1 molar ratio in refluxing dry benzene. Plausible structures of these complexes were suggested with the aid of physicochemical and spectroscopic studies. 119Sn NMR spectral data revealed the presence of a hexacoordinated tin centre in these dimethyltin(IV) complexes. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

15.
A set of pentacoordinated dimethyltin(IV) complexes of flexible N‐protected amino acids and fluorinated β‐diketone/β‐diketones was screened for their antibacterial activity against Pseudomonas aeruginosa , Staphylococcus aureus and Streptomyces griseus . These pentacoordinated complexes of the type Me2SnAB (where : R = CH(CH3)C2H5, A1H; CH2CH(CH3)2, A2H; CH(CH3)2, A3H; CH2C6H5, A4H; and BH = R'C(O)CH2C(O)R″: R′ = C6H5, R″ = CF3, B1H; R′ = R″ = CH3, B2H; R′ = C6H5, R″ = CH3, B3H; R′ = R″ = C6H5, B4H) were generated by the reactions of dimethyltin(IV) dichloride with sodium salts of flexible N‐protected amino acids (ANa) and fluorinated β‐diketone/β‐diketones (BNa) in 1:1:1 molar ratio in refluxing dry benzene solution. Plausible structures of these complexes were elucidated on the basis of physicochemical and spectral studies. 119Sn NMR spectral data revealed the presence of pentacoordinated tin centres in these dimethyltin(IV) complexes.  相似文献   

16.
The formation constants of the species formed in the systems H+ + dimethyltin(IV) + 5′‐IMP and 5′‐UMP, H+ + 5′‐IMP and H+ + 5′‐UMP have been determined in aqueous solution in the pH range 1.5–9.5 at constant temperature (25 °C) and constant ionic strength (0.1 mol dm−3 NaClO4), using spectrophotometric and potentiometric techniques. 1H and 31P NMR investigations in aqueous solution confirmed the species formation. The precipitated complexes of IMP and UMP by Me2Sn(IV)2+ at low pH values were characterized by elemental analysis and FTIR spectroscopy methods, the bonding sites of the ligands were determined and ruled out purine and pyrimidine moieties (N‐7 and N‐1 in IMP and N‐3 in UMP, respectively) while a bidentated coordination of the phosphate group is concluded in both cases. Finally, the experiments revealed the existence of complexes with trigonal bipyramidal structures that is in agreement with similar systems resulted previously. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

17.
Some five-coordinated dimethyltin(IV) complexes of the type Me2SnL (where L is the anion of a bifunctional tridentate Schiff base) were synthesized. These Schiff bases are N-(3-hydroxypyridine-2-yl)-3-methoxysalicylideneimine, HOC6H3OCH3CH=NC5H3NOH (1), N-(3-hydroxypyridine-2-yl)-3-ethoxysalicylideneimine, HOC6H3OC2H5CH=NC5H3NOH (2), N-(3-hydroxypyridine-2-yl)-5-chlorosalicylideneimine, HOC6H3ClCH=NC5H3NOH (3), and N-(3-hydroxypyridine-2-yl)-3-methoxy-5-bromosalicylideneimine, HOC6H2OCH3BrCH=NC5H3NOH (4). Dimethyltin(IV) complex of 3 (3a) was characterized by single crystal X-ray diffraction method and a coordination geometry that is nearly halfway between trigonal–bipyramidal and square pyramidal arrangement was found. Dimethyltin complexes of (1), (2), and (4) were also prepared and characterized by the comparison of their elemental analysis and 1H-NMR-, IR-, UV- and mass spectral data with those of (3a). For example, in the 1H-NMR spectra, the 2J(119Sn-1H) in the Sn-CH3 moiety have values between 80 Hz and 90 Hz, typical of five-coordinated tin species. By using these values in Lockart’s Equations, H3C–Sn–CH3 angles in the complexes were estimated to lie between 130° and 145°. X-ray diffraction value for 3a, confirms this estimate within 3.4% relative deviation (129.7° exp. Vs. 134.9° estimate).  相似文献   

18.
Interaction of dipropyltin(IV) with selected amino acids, peptides, dicarboxylic acids or DNA constituents was investigated using potentiometric techniques. Amino acids form 1?:?1 and 1?:?2 complexes and, in some cases, protonated complexes. The amino acid is bound to dipropyltin(IV) by the amino and carboxylate groups. Serine is complexed to dipropyltin(IV) with ionization of the alcoholic group. A relationship exists between the acid dissociation constant of the amino acids and the formation constants of the corresponding complexes. Dicarboxylic acids form both 1?:?1 and 1?:?2 complexes. Diacids forming five- and six-membered chelate rings are the most stable. Peptides form complexes with stoichiometric coefficients 111(MLH), 110(ML) and 11-1(MLH?1)(tin: peptide: H+). The mode of coordination is discussed based on existing data and previous investigations. DNA constituents inosine, adenosine, uracil, uridine, and thymine form 1?:?1 and 1?:?2 complexes and the binding sites are assigned. Inosine 5′-monophosphate, guanosine 5′-monophosphate, adenosine 5′-monophosphate and adenine form protonated species in addition to 1?:?1 and 1?:?2 complexes. The protonation sites and tin-binding sites were elucidated. Cytosine and cytidine do not form complexes with dipropyltin(IV) due to low basicity of the donor sites. The stepwise formation constants of the complexes formed in solution were calculated using the non-linear least-square program MINIQUAD-75. The concentration distribution of the various complex species was evaluated as a function of pH.  相似文献   

19.
《Polyhedron》1999,18(26):3417-3424
Four macrocyclic trans-dioxo-tetraamines containing sulphur or oxygen as additional donors have been prepared: 1-oxa-3,14-dioxo-4,7,10,13-tetraazacyclopentadecane, 1-thia-3,14-dioxo-4,7,10,13-tetraazacyclopentadecane, 1-oxa-3,16-dioxo-4,8,11,15-tetraazacycloheptadecane and 1-thia-3,16-dioxo-4,8,11,15-tetraazacycloheptadecane. Their protonation as well as their metal binding properties with Cu2+ and Ni2+ have been determined at 25°C in 0.10 mol dm−3 KNO3. The complexation process was investigated by potentiometric, calorimetric and UV/VIS-spectroscopic titrations. IR-spectroscopy was used to establish the involvement of the amido groups in the coordination. Oxidation of the complexes to the trivalent state of the metal ion was also investigated by cyclic voltammetry. Metal ion complexation promotes the deprotonation of the amide nitrogens, resulting in a neutral complex with four nitrogen donors and a MLH-2 stoichiometry at pH 8. Additional complexes with stoichiometry ML and MLH-1 were needed to describe the complexation in the pH range 2–11. Their stability constants were calculated. The presence of oxygen or sulphur donors as well as ring enlargement influence the complexation properties. The electronic spectra indicate rather distorted tetragonal coordination geometries for the Cu(II)-complexes. The Ni(II)-complexes are all square–planar with the exception of an equilibrium between a square–planar and an octahedral form for NiL1H−2. All complexes are easily but irreversibly oxidized to the trivalent state of the metal ion.  相似文献   

20.
Series of new trigonal bipyramidal and octahedral complexes of tin(IV) have been synthesized by the reaction of dimethyltin(IV) dichloride with 4-nitro-benzanilidethiosemicarbazone (L(1)H), 4-chlorobenzanilidethiosemicarbazone (L(2)H), 4-nitrobenzanilidesemicarbazone (L(3)H) and 4-chlorobenzanilidesemicarbazone (L(4)H). The unimolecular and bimolecular reactions of dimethyltin(IV) dichloride and monobasic bidentate ligands were carried out using microwave irradiations as the thermal energy source and the complexes so formed were characterized by elemental analysis, conductance measurements, molecular weight determinations and spectral data, viz. IR, UV-vis, (1)H and (13)C NMR. The complexes have also been prepared by the general thermal methods for comparison purposes. The comparison data support the synthesis using the microwave route, i.e. green chemistry route. The tin(IV) complexes show penta-coordinated structure for 1:1 complexes and hexa-coordinated for 1:2 complexes. The antifungal, antibacterial and antifertility activities have been examined and the results were indeed very encouraging.  相似文献   

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