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1.
Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution. I. A Polyazapolyoxa Cylindrical Macrotricycle and its Monocyclic Subunit pH-metry and UV spectrophotometry were used to study the complexing properties of the cylindrical macrotricycle, 1,7,13,19-tetraaza-4,16-dioxa-10,22,27,32-tetraoxatricyclo[17.5.5.5]tetratriacontane ( 1 ) and of its constitutive monocyclic subunit, 1,7-diaza-4,10-dioxacyclododecane ( 2 ) with some transition and heavy metal cations (Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, Ag+), in aqueous medium 0.1M Et4NClO4, at 25°. The protonation constants of the ligands as well as the nature and the stabilities of the complexes formed in the pH-regions studied were determined. The tricycle 1 only formed dinuclear M2L complexes with Cu2+, Zn2+, and Ag+, accompanied in the latter case by a protonated mononuclear MLH species, and with Cu2+ and Zn2+ at high pH-values by dinuclear hydroxo complexes. Only mononuclear complexes were evidenced with the other cations, ML being accompanied either by protonated or hydroxy mononuclear species. The mononuclear complexes of 1 , when they existed, were more stable than the corresponding complexes of 2 , except for cobalt which formed complexes of comparable stability with both ligands. In the other cases (Cd2+, Pb2+, Ag+), the stability differences between the complexes of 1 and 2 increased with the size of the cation.  相似文献   

2.
Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution III. The Monocycle [22]-Py2N4 The nature and stability of complexes formed by a new 22-membered monocycle L = [22]-Py2N4 with the cations Mn+ = Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, and Ag+ have been determined in aqueous solutions (0.01M NaClO4, 25°) by pH-metry and also, for the copper system, by UV-absorption spectrophotometry. The stepwise protonation constants of the four amine functions of L were 9.1, 8.3, 7.1 and 3.7 logarithms units, respectively. No evidence was found for the protonation of the two pyridine nitrogen atoms. Mononuclear complexes MLn+ were identified in all systems investigated, but the dinuclear species M2L2n+ were only found with Cu2+ and Ag+. The logarithms of the overall stability constants for the copper and silver complexes are CuL2+, 12.9; Cu2L4+, 18.6; Agl+, 6.3; Ag2L2+, 10.9, respectively. Mononuclear hydroxy species MLOH(n?1)+ were identified in all systems except those of copper and silver. No dinuclear hydroxy complexes were detected. The complexing properties of L are compared to those of the large and less rigid bis-dien.  相似文献   

3.
Stability in Methanol and Thermodynamic Transfer Properties of the Cryptates of some Transition Cations and Heavy Metals The nature and stability of the macrocyclic and macrobicyclic complexes of Ag+, Cd2+, and Pb2+ (Mn+) with 21, 22, 211, 221 and 222 in anhydrous methanol 0.05M in Et4N+ClO?4, at 25° (see Scheme) have been determined by potentiometry and spectrophotometry. Binuclear complexes M2L2n+ have been observed in all cases, besides the mononuclear MLn+ complexes. The macrobicyclic 1:1 complexes MLn+ exhibit an important ‘cryptate effect’ with Mn+=Ag+, Pb2+ and Cd2+, but not with Cu2+ and Zn2+; their stability is in all cases maximum with 221. The applicability to our results of the recent extrathermodynamic hypothesis involving MLn+ cryptates is examined.  相似文献   

4.
Stability constants for aqueous Ag+/Br?, Ag+/SCN?, and mixed Ag+/Br?/SCN? complexes are determined at 25° C by using data generated potentiometrically in solutions having ionic strengths of 0.4, 1.0, and 2.0 m. Monte Carlo numerical methods which yield apparent stability constants for these complexes as well as confidence limits are described in detail. Explicit consideration of speciation shows that under useful precipitation conditions (high bromide and low thiocyanate), a significant fraction of soluble silver is present as AgBrn (SCN)1?n?mm complexes. The most prevalent mixed complexes under these conditions are AgBr (SCN)? (log β11=8.0 ± 0.5) and AgBr2(SCN)2? (log β21=9.2 ± 0.3). The free energies of formation of the other tri- and tetra-coordinate mixed complexes are nearly indistinguishable (log β12=9.3 ± 0.5; log β31=9.0 ± 0.6; log β22=9.6 ± 0.9; log β13=10.3 ±0.5).  相似文献   

5.
The electronic structures of the 4-4 SBU, the β-cage, and the β-cage with two 4-4 SBU's attached to it have been studied by means of EH-MO calculations. No indication of the formation of a band structure has been found. The HOMO region consists of many closely spaced, localized states, 98.6% of them concentrated on the O-atoms. Reversible color changes of Cu+1 and Ag+1 zeolites observed upon hydration-dehydration experiments can be understood as charge-transfer transitions from the HOMO concentrated on the zeolite O-atoms to the metal cations. As soon as the Cu+1 or Ag+1 are partially hydrated, the ns* and np* states are shifted to higher energies. The luminescence observed with dehydrated Cu+1-zeolites X is caused by a 4p*←HOMO absorption, followed by spontaneous 4s*←4p* emission. After a detailed study of a Cu+1 in the 6-6 SBU, we discuss the electronic structure of a β-cage filled with 1,2,4,8, and 9 Cu+1. In each case, the β-cage is found to be too small to allow the formation of a band structure. The levels caused by the added copper are distinctly quantized. Calculations on [Ag3(H2O)3]3+ in a β-cage are reported. The direct interaction between the Ag-atoms is significant. As a consequence, the states formed by Ag 5s and 5p atomic orbitals are delocalized over the three Ag-centers. In both the Cu+1 and the Ag+1 zeolites, the ligand-field picture is found to be insufficient to explain the electronic structure, when the metal is coordinated to the zeolite oxygen framework.  相似文献   

6.
Stability in aqueous solution of some complexes of heavy metals with diaza-polyoxamacrocyclic ligands Stability of metal complexes (Mn+ = Cu2+, Ni2+, Co2+, Zn2+, Pb2+, Ag+ and Cd2+) with five diaza-polyoxamacrocycles (L = [2.1.1], [2.2.1], [2.2.2], [2.1] and [2.2] ) have been determined at 25°, in 0.1 M Et4N+ClO aqueous solutions, by means of potentiometric titrations. All cations form MLn+ complexes; Cu2+ also forms the MHL(n+1)+ protonated species with both [2.2.1] and [2.1.1] ligands. The stability of these complexes has been discussed in terms of structure and by considering the ionic radii of the cations together with the radii of the macrocyclic cavities. Different behaviour is observed between some of these complexes and the well known alkali and alkaline-earth cryptates, partly due to the more covalent nature of bonds formed by the investigated cations and the donor sites of the ligands. The effect of the substitution of two oxygen by two sulfur atoms in the pentadentate ligand [2.1] on the stability of the complexes is reported.  相似文献   

7.
Speciation diagrams and stability constants for glutamate (Glu) with (Cr3+) and (Cu2+) in aqueous solutions are presented. The current study covers a larger pH-range affording accurate results, and reveal a different set of species for Cu2+ and species not previously reported for Cr3+. For the Cu2+ Glu system, the most successful model that refined the potentiometric data contains the simple one-to-one complex, the bis-complex and the mono-hydroxo complex. The overall stability constants for Cu2+–Glu complexes have respective values of log β110 = 7.6 ± 0.2, log β11-1 = 1.3 ± 0.7, log β120 = 13.6 ± 0.2. Attempts to refine the stability constant for the mono-protonated metal complex (log β111) that was reported in the literature indicated that this mono-protonated species did not form to an appreciable amount to be important for the model presented here. For the Cr3+ Glu system, the overall stability constants for the complexes formed have the values of log β110 = 8.34 ± 0.03, log β11-1 = 1.9 ± 0.1 and log β11-2 = ?4.6 ± 0.1. These results for Cr3+ system covers wider pH-range and have more accuracy than those reported previously. The NMR experiments for Glu revealed downfield shifts of all protons as pH values decrease from 11.21 to 2.85.  相似文献   

8.
We demonstrate a new material by intercalating Mo3S132? into Mg/Al layered double hydroxide (abbr. Mo3S13-LDH), exhibiting excellent capture capability for toxic Hg2+ and noble metal silver (Ag). The as-prepared Mo3S13-LDH displays ultra-high selectivity of Ag+, Hg2+ and Cu2+ in the presence of various competitive ions, with the order of Ag+>Hg2+>Cu2+>Pb2+≥Co2+, Ni2+, Zn2+, Cd2+. For Ag+ and Hg2+, extremely fast adsorption rates (≈90 % within 10 min, >99 % in 1 h) are observed. Much high selectivity is present for Ag+ and Cu2+, especially for trace amounts of Ag+ (≈1 ppm), achieving a large separation factor (SFAg/Cu) of ≈8000 at the large Cu/Ag ratio of 520. The overwhelming adsorption capacities for Ag+ (qmAg=1073 mg g?1) and Hg2+ (qmHg=594 mg g?1) place the Mo3S13-LDH at the top of performing sorbent materials. Most importantly, Mo3S13-LDH captures Ag+ via two paths: a) formation of Ag2S due to Ag-S complexation and precipitation, and b) reduction of Ag+ to metallic silver (Ag0). The Mo3S13-LDH is a promising material to extract low-grade silver from copper-rich minerals and trap highly toxic Hg2+ from polluted water.  相似文献   

9.
The different coordination behavior of the ligand tBuN=Te(μ-NtBu)2Te=NtBu (L) towards Cu+ and Ag+ results from a cistrans isomerization. The two Cu+ ions in [Cu2L3]2+ (shown schematically) bridge trans and cis isomers of the ligand, whereas the Ag+ ions in [Ag2L2]2+ link two trans ligands and exhibit a weak Ag⋅⋅⋅Ag interaction.  相似文献   

10.
Efforts to improve agricultural productivity have led to a growing dependency on organophosphorus pesticides. Phosphorothioate and phosphorodithioate pesticides are organophosphorus pesticide subclasses with widespread application for the control of insects feeding on vegetables and fruits. However, even low doses of these pesticides can cause neurological problems in humans; thus, their determination and monitoring in agricultural foodstuffs is important for human health. Phosphorothioate and phosphorodithioate pesticides may be poorly ionized during electrospray, adversely affecting limits of detection. These pesticides can form complexes with Cu2+ and Ag+, however, potentially improving ionization. In the present work, we used electrospray ionization/mass spectrometry (ESI/MS) to study fenitrothion, parathion, diazinon, and malathion coordination complexes with silver and copper ions. Stable 1 : 1 and 1 : 2 metal/pesticide complexes were detected. Mass spectra acquired from pesticide solutions containing Ag+ or Cu2+ showed a significant increase in signal‐to‐background ratio over those acquired from solutions containing only the pesticides, with Ag+ improving detection more effectively than Cu2+. Addition of Ag+ to a pesticide solution improved the limit of detection by ten times. The relative affinity of each pesticide for Ag+ was related to complex stability, following the order diazinon > malathion > fenitrothion > parathion. The formation of Ag+–pesticide complexes can significantly improve the detection of phosphorothioate and phosphorodithioate pesticides using ESI/MS. The technique could potentially be used in reactive desorption electrospray ionization/mass spectrometry to detect phosphorothioate and phosphorodithioate pesticides on fruit and vegetable skins. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

11.
Macrocyclic Complexes of Lanthanides: Stability and Electrochemical Behaviour in Methanol and Propylene Carbonate The stabilities of the 1:1 complexes of the trivalent lanthanides with the diazapolyoxamacrocycles (2.1.) and (2.2.1.) in anhydrous methanol and propylene carbonate have been determined at 25°, by competitive potentiometric methods using H+ or Ag+ as auxiliary cations, with Et4NClO4 as supporting-electrolyte. Additional data are also reported for the crown ethers 15C5 and 18C6 in propylene carbonate. It is shown that the diazapolyoxamacrocycles are much stronger complexing agents for trivalent lanthanides than macrocyclic polyethers, and that the bicyclic (2.2.1.) cryptates are more stable than the monocyclic (2.1.) complexes. With increasing atomic number of the lanthanides, the stability increases with diazapolyoxamacrocycles and decreases with cyclic polyethers. The electrochemical reduction of the trivalent samarium and europium cryptates has been investigated by polarography on a dropping Hg-electrode, in water and methanol. In both solvating solvents, the +2 oxidation states of the cations are stabilized by complexation.  相似文献   

12.
8‐Hydroxyquinolium chloroacetate ( L1 ) was synthesized and characterized. The results suggest that L1 loses ethyl chloroacetate ion on coordination at low pH (2–5) and consequently it behaves as 8‐hydoxyquinoline ( L2 ). Cu2+, Co2+, Pt4+, Pd2+, Au3+, Ag+ and Nd3+ complexes derived from L2 have been synthesized and characterized using spectral, magnetic and thermal measurements. L2 acts as a neutral bidentate ligand in the case of Cu2+, Co2+, Pt4+, Pd2+ and Nd3+ complexes and as a mononegative bidentate ligand in the case of Au3+ and Ag+ complexes. Octahedral geometry is proposed for Cu2+, Co2+ (grey) and Pt4+ complexes and square‐planar for Co2+ (green), Pd2+ and Au3+ complexes. The bond lengths, bond angles, chemical reactivities, binding energies and dipole moments for all compounds were evaluated using density functional theory and molecular electrostatic potential for L1 . Superoxide dismutase radical scavenger‐like activity and cytotoxic activity of the complexes towards HepG2 liver cancer cells has been screened. Cytotoxicity measurements show that Ag+ and Pd2+ complexes have the highest cytotoxic activity while L1 , Cu2+, Co2+ (grey), Co2+ (green), Pt4+ and Nd3+ complexes have no cytotoxic activity. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

13.
The iiii stereoisomer of the tetrathiophosphonate-calix[4]resorcinarene host 1 exhibited excellent extraction properties towards soft metal ions, with a better affinity for Ag+ (91%), than for Tl+ (38%) and Hg2+ (16%). The extraction of other picrate salts (Cu2+, Ni2+, Co2+, Zn2+, Cd2+, Pb2+) was not detected. The stoichiometry and the structure of the Hg2+, Tl+ and Ag+ complexes were studied by NMR in solution and gave respectively 1:1, 1:1 and 1:2 host-guest complexes. The formation of the self-assembled 12·(AgPic)4 complex was independent on the anion and only observed with silver(I) ion.  相似文献   

14.
Lipophilic Tetraazamacrocyles: Extraction of Metal Ions by Impregnated Resin Extraction of Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+ and Ag+ by lipophilic tetraazamacrocycles dispersed on a solid matrix (Amberlite XAD7) is reported. Extraction efficiency is sensitive to the metal ion identity and the cavity size of the macrocycle. The influence of kinetic factors upon extraction efficiency is discussed.  相似文献   

15.
The composition and the stability constants of the complexes formed between Ag(I) and ligands of the type where n,m = 2,2; 2,3; 2,4; 3,3; 3,4; 4,4, have been determined by a pH/pM-metric method at 25°C in a 0.5 M (K)NO3 medium. The determination of the stability constants proceeded by a combination of a graphical method and a least squares minimization procedure. The complex formation is discussed in comparison with silver complexes formed with S-containing mono-amines and in terms of the Taft σ*-parameters for the substituents. Below pH = 4, the protonated complexes AgLH23+ and AgL2H45+ are formed and the thioethergroup is the only coordinating centre. In neutral and alkaline medium there was evidence for the species AgLH2+, Ag2L2H24+, Ag2L2H3+, Ag2L22+, AgL2H34+, AgL2H2+, AgL2 + and Ag2L2+ in which Ag+? S and Ag+? NH2 bonds are involved. It is shown that in the Ag2L22+ and Ag2L2+ complexes the ligands effectively coordinate through all available donor centres.  相似文献   

16.
The complexation of Ag+ ions with anions of β-lactam antibiotics, such as benzylpenicilline (Bzp?) and oxacilline (Oxa?), in aqueous solution at 25°C and an ionic strength of 0.1 (KNO3) was studied potentiometrically using a silver indicator electrode. The formation constants of the complexes AgBzp (logβ = 2.21 ± 0.01), AgBzp 2 ? (logβ = 3.91 ± 0.02), Ag2Oxa+ (logβ = 4.89 ± 0.01), AgOxa (logβ = 2.88 ± 0.01), (logβ = 5.43 ± 0.01) were determined.  相似文献   

17.
The role of hydrogen bonding in the chemistry of transition‐metal complexes remains a topic of intense scientific and technological interest. Poly(acrylo‐amidino diethylenediamine) was synthesized to study the effects of hydrogen bonding on complexes at different pHs. The polymer was synthesized through the coupling of diethylene triamine with polyacrylonitrile fiber in the presence of AlCl3 · 6H2O addition. The adsorption capacity of this polymer was 11.4 mequiv/g. The ions used for the adsorption test were CrO, PO, Cu2+, Ni2+, Fe2+, and Ag+. All experiments were confirmed with Fourier transform infrared. In the study of anion adsorption, at low pHs, only ionic bonds existed, whereas at high pHs, no bonds existed. However, in the middle pH region, both ionic bonds and hydrogen bonds formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion or phosphate ion. When poly(acrylo‐amidino diethylenediamine) and metal ions (Cu2+, Ni2+, Fe2+, and Ag+) formed complexes, a hydrogen‐bonding effect was not observed with Fourier transform infrared. The quantity of metal ions adsorbed onto poly(acrylo‐amidino diethylenediamine) followed the order Ag+ > Cu2+ > Fe2+ > Ni2+. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2010–2018, 2004  相似文献   

18.
The complexes of the peptides (Pep) bradykinin (RPPGFSPFR), des-Arg1-bradykinin, and des-Arg9-bradykinin with the metal (M) ions Na+, K+, Cs+, Cu+, Ag+, Co2+, Ni2+, and Zn2+ are generated in the gas phase by matrix-assisted laser desorption/ionization and the structures of the corresponding [Pep + M+]+ or [Pep − H+ + M2+]+ cations are probed by postsource decay (PSD) mass spectrometry. The PSD spectra depend significantly on the metal ion attached; moreover, the various metal ions respond differently to the presence or absence of a basic arginine residue. The Na+ and K+ adducts of all three peptides mainly produce N-terminal sequence ions upon PSD; the fragments observed point out that these metal ions are anchored by the PPGF segment and not the arginine residue(s). In contrast, the adducts of Cu+ and Ag+ show a strong dependence on the position of Arg; complexes of des-Arg1-Pep (which contains a C-terminal Arg) produce primarily yn ions whereas those of des-Arg9-Pep generate exclusively an and bn ions. These trends are consistent with Cu+ ligation by Arg’s guanidine group. The [Pep + Cs+]+ ions mainly yield Cs+; a second significant fragmentation occurs only if a C-terminal arginine is present and involves elimination of this arginine’s side chain plus water. This reaction is rationalized through a salt bridge mechanism. The most prominent PSD products from [Pep − H+ + Co2+]+ and [Pep − H+ + Ni2+]+ contain at least one phenylalanine residue, revealing a marked preference for these divalent metal ions to bind to aromatic rings; the fragmentation patterns of the complexes further suggest that Co2+ and Ni2+ bind to deprotonated amide nitrogens. The coordination chemistry of Zn2+ combines features found with the divalent Co2+/Ni2+ as well as the monovalent Cu+/Ag+ transition metal ions. Generally, the structure and fragmentation behavior of each complex reflects the intrinsic coordination preferences of the corresponding metal ion.  相似文献   

19.
Three novel thiaazacrown ethers 1, 2 and 3 were synthesized in a simple way and in high yield. The complex formation between Ag+, Cu2+, Zn2+, Pb2+, Hg2+ and Cd2+ metal cations with thiaazacrown ethers 1, 2 and 3 have been studied in acetonitrile:chloroform (1:1) binary solvent system using conductometric technique. The conductance data show that the stochiometry of the complexes with Ag+, Cu2+ and Zn2+ cations is 1:1 (L:M), but in the case of Pb2+ and Hg2+ cations, a 1:2 (L:M) complex is formed in solutions. The formation constants of the resulting 1:1 complexes were determined from the molar conductance-mole ratio data at 25 °C. It was found that the stability constants of 1-Ag2+, 2-Ag+ and 3-Ag+ complexes are higher than those of their corresponding Zn2+ and Cu2+ complexes and found to vary in order 2 for Ag+.  相似文献   

20.
The complexation reaction between Tl+, Ag+ and Pb2+ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand in acetonitrile (ACN)–H2O and methanol (MeOH)–H2O binary solutions has been studied at different temperatures using conductometric method. The conductometric data show that the stoichiometry of the complexes is 1: 1 [M: L] and the stability constant of complexes changes with the binary solutions identity. Also, the structure of the resulting 1: 1 complexes was optimized using the LanL2dz basis set at the B3LYP level of theory using GAUSSIAN03 software. The results show that the change of logKf for (DFMP.Pb)2+ and (DFMP.Ag)+ complexes with the mole ratio of acetonitrile and for (DFMP.Ag)+ and (DFMP.Tl)+ complexes with the mole ratio of methanol have a linear behavior, while the change of logKf of (DFMP.Tl)+complex in ACN–H2O binary solutions (with a minimum in XACN = 0.5) and (DFMP.Ag)+ complex in MeOH–H2O binary solutions (with a minimum in XMeOH = 0.75) show a non-linear behavior. The selectivity order of DFMP ligand for these cations in mol % CAN = 25 and 75 obtain Tl+ > Pb2+ > Ag+ but in mol % CAN = 50, the selectivity order observe Pb2+ > Tl+ > Ag+. Also, this selectivity sequence of DFMP in MeOH–H2O (mol % MeOH = 75 and 100) and (mol % MeOH = 50) is obtained Pb2+ > Ag+ and Tl+ > Ag+ > Pb2+ respectively. The values of thermodynamic parameters show that these values are influenced by the nature and the composition of binary solution. In all cases, the resulting complexes are enthalpy stabilized and entropy destabilized. The TΔSC° versus ΔHC° plot of all obtained thermodynamic data shows a fairly good linear correlation which indicates the existence of enthalpy-entropy compensation in the complexation reactions.  相似文献   

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