Stereoselective Formation of Ternary Copper(II) Complexes of (S)-Amino-acid Amides and (R)- or (S)-Histidine and (R)- or (S)-Tyrosine in Aqueous Solution

Formation constants of ternary complexes of Cu^II with (S)-amino-acid amides ((S)-phenylalaninamide, (S)-prolinamide, and (S)-tryptophanamide) and (R)- or (S)-histidine and (R)- or (S)-tyrosine were determined potentiometrically in aqueous solution. Significant stereoselectivity was presented by all three amides towards histidine, the diastereoisomeric complexes with ‘heterochiral’ ligands being more stable than those with ‘homochiral’ ligands (see Table 3). The stereoselectivity observed with (S)-phenylalaninamide and (S)-tryptophanamide may be explained on the basis of hydrophobic stacking interactions between 1H-imidazole and the aromatic side chain, favoured by the terdentate behaviour of histidine (see Fig.2), whereas repulsive effects seem to be prevalent with (S)-prolinamide. Only (S)-prolinamide and (S)-phenylalaninamide show appreciable stereoselectivity with tyrosine, which is bidentate, probably on account of repulsive interactions. The present results on the stability of ternary complexes in solution allow to draw some conclusions on the mechanism of chiral discrimination performed by Cu^II complexes of (S)-amino-acid amides added to the mobile phase in HPLC (reversed phase).     

Copper(II) ion hydrolysis in aqueous solution

A copper(II) ion-selective-electrode potentiometric method was used to determine the first and second hydrolysis constants of Cu²⁺. Special techniques prevented copper(II) hydroxide precipitation, and copper(II) carbonate and cipper(II) organic complexation during the titration of the experimental solution over the pH range 6.8–8.4. The large change in the total copper concentration during the titration due to adsorption of copper onto the vessel walls was accounted for by measuring the total copper concentration at each pH by atomic absorption spectrophotometry. The two hydrolysis constants were determined at 25°C in 0.7 and 0.05m NaClO₄ media. The measured stability constants are independent of the copper concentration and yield similar zero ionic strength values. Also, the stepwise equilibrium constants decrease as the ligand number increases.     

Copper(II) complexes of diaminodiamides in aqueous solution

The basicity constants of N,N′-bis(β-carbamoylethyl)ethylenediamine, N,N′-bis(β-carbamoylethyl)trimethylenediamine, N,N′-bis(β-carbamoylethyl)-1,2-propylenediamine, and N,N′-bis-(β-carbamoylethyl)-2-hydroxyltrimethylenediamine were determined potentiometrically in 0.10 mol dm^?3 NaNO₃ at 25.0°C. The formation of Cu(II) complexes of these ligands and the CuO to CuN bond rearrangements at the two amide sites of these complexes were investigated quantitatively by potentiometric and spectrophotometric techniques under the same conditions. Electronic spectra of the Cu(II) complexes of these ligands and their deprotonated species formed in aqueous solution were measured and discussed.     

Binary and Ternary Complexes Involved in the Systems Methioninehydroxamic Acid - Glycylglycine - Ni(II) or Cu(II) Ions

The formation constants of binary and ternary complexes involved in the systems methioninehydroxamic acid (MX), glycylglycine (GG) and Cu(II) or Ni(II) were determined by pH-metric titration in aqueous solution at an ionic strength (I)= 0.15 M NaCl) and T = 25°C. Ternary species of the type (MX : GG : Ni(II) or Cu(II) : H) = (1 : 1 : 1 : r), (2 : 1 : 1 : r) and (1 : 2 : 1 : r) exist in the pH range ～3 to ～10. Differential pulse polarography (DPP) was used to follow complex formation and to study the reduction properties of these metal ions in the presence of MX, and GG. The metal oxidation states were more stabilized in the ternary systems than in the binary systems except for a few Ni(II) systems. Spectral studies in the UV-Vis-nIR were used to monitor the presence of ternary species in the Ni(II) and Cu(II) systems. In addition, EPR studies were also used to record the magnetic properties of the binary and ternary species in the Cu(II) systems.     

Stereoselective synthesis of pinane-based β- and γ-amino acids via conjugate addition of lithium amides and nitromethane

Michael addition of dibenzylamine to (?)- and (+)-tert-butyl myrtenate, (?)-2 and (+)-2, derived from (?)- and (+)-myrtenal, furnished monoterpene-based β-amino acid derivatives in highly stereospecific reactions. The resultant amino esters (?)-3 and (+)-3 were transformed to unsubstituted, mono- and disubstituted and Fmoc-protected amino acids (?)-6-11 and (+)-6-11, which are promising building blocks for the synthesis of β-peptides and 1,3-heterocycles. The microwave-assisted conjugate addition of nitromethane to α,β-unsaturated esters (?)-12 and (+)-12 likewise resulted in nitro esters (?)-13 and (+)-13 in highly stereospecific reactions. Compounds (?)-13 and (+)-13 were successfully transformed into γ-amino acids (?)-16 and (+)-16 in two steps.     

Complex formation equilibria of L-Amino-Acid amides with copper(II) in aqueous solution

Protonation and Cu(II) complexation equilibria of L -phenyhilaninamide, N²-methyl-L-phenylalaninamide, N², N²-dimethyl-L-phenylalaninamide, L -valinamide, and L -prolinamide have been studied by potentiometry in aqueous solution. The formation constants of the species observed, CuL²⁺, CuL, CuLH, CuL₂H and CuL₂H_?2, are discussed in relation to the structures of the ligands. Possible structures of bisamidato complexes are proposed on the ground of VIS and CD spectra. Since Cu(II) complexes of the present ligands (pH range 6–8) perform chiral resolution of dansyl- and unmodified amino acids in HPLC (reversed phase), it is relevant for the investigation of the resolution mechanism to know which are the species potentially involved in the recognition process.     

Cadmium(II) and Mercury(II) Complexes in Ternary Systems with Cytidine and Diamines or Triamines

The mode of coordination of complexes formed in the systems Cd(II) or Hg(II)/cytidine/di- or triamine is proposed on the basis of equilibrium and spectroscopic studies. Mercury(II) binds much more strongly to cytidine and polyamine (PA) than cadmium. It was found from equilibrium and 13 C NMR studies that in the Hg(II) and Cd(II)/ Cyd /di- or triamine complexes, metallation mainly involves the N(3) atom of the pyrimidine base of the nucleoside and m NH x + groups from PA. In MLL' complexes of both metals with diamines, all available donor nitrogen atoms of the polyamine are involved in coordination. In analogous systems with triamines, interaction of all nitrogen atoms is observed for Cd(II) systems as well as in the Hg( Cyd )(2,3- tri ) species. Only two nitrogen atoms of the polyamine coordinate in ternary Hg(II) complexes with dien, 3,3-tri and Spd .     

Copper (II) adsorption from aqueous solution by herbaceous peat

In this research, the herbaceous peat collected from Gavurgolu peatlands, one of the biggest Turkish peatlands, was utilized as an adsorbent for the removal of copper (II) ions from aqueous solution. Adsorption experiments were conducted under various conditions, i.e., initial concentration, temperature, and pH. While the amount of Cu (II) adsorbed on the peat increased with increasing concentration of Cu (II) ions, it was not markedly affected by temperature and pH. Percentage removal was higher at lower concentration. For example, the maximum percentage removal of Cu (II) ions for initial concentration of 3 x 10(-4) M was 97.04% at 21 degrees C and pH 5.5. The adsorption capacity (Q(0)) of the peat was 4.84 mgg(-1) from Langmuir adsorption isotherm for the concentration range of 3 x 10(-4)-6 x 10(-4) M at 21 degrees C and pH 5.5. The equilibrium time of adsorption of Cu (II) ions was 150 min and independent of concentration and temperature. The amount of Cu (II) adsorbed at equilibrium time did not considerably change with temperature and pH. It was also determined that adsorption isotherm followed both Freundlich and Langmuir. Uptake mechanism of Cu (II) ions by the peat occurs via cation exchange (especially by means of Ca(2+) and Mg(2+)) as well as copper/peat complexation. Adsorption kinetic was consistent with the pseudo-second-order model.     

Copper(II)-catalyzed oxidation of d-alpha-tocopherol by oxygen in aqueous solution

alpha-Tocopherol (alpha-Toc) was solubilized in aqueous solutions using 13 solubilizing agents and the products of oxidation by oxygen in the presence and the absence of Cu(II) were analyzed by HPLC. In the presence of Cu(II), the oxidation was accelerated and 5-formyl-7,8-dimethyltocol and alpha-tocoquinone were the major oxidation products. Their yields greatly increased in the presence of Cu(II). The yields and the rates of formation of the products were dependent on the properties of solubilizing agents and other conditions as well as the presence of Cu(II) or other metal ions. It is suggested that slight changes in the structure of the solubilizing agents affect the course of the reaction.     

Formation of (9-adeninyl)-ω-cyanoalkanes from (9-adeninyl)-α-amino acids

Elimination of CO₂ and oxidation of the amino group of the amino acid to give the corresponding (9-adeninyl)--cyanoalkanes occur under the conditions of bromination of (9-adeninyl)--amino acids in both alkaline and buffer solutions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 539–541, April, 1982.     

Stereoselective synthesis of novel conformationally restricted β- and γ-amino acids

Novel conformationally restricted β- and γ-amino acids containing a cyclopropane ring could be stereoselectively synthesized from readily available 5-methoxyindole and pyridine by copper(I)-catalyzed cyclopropanation with methyl diazoacetate followed by subsequent oxidative cleavage of the resulting adducts.     

Stereoselective synthesis,solution structure and metal complexes of (1S,2S)-2-amino-1-hydroxyalkylphosphonic acids

The highly stereoselective synthesis of (1S,2S)-2-amino-1-hydroxyalkylphosphonic acids was achieved by addition of dimethyl phosphite to N-protected aminoaldehydes. Relative configuration and solution conformations of (1S,2S)-2-amino-1-hydroxy-alkylphosphonic acids (in D₂O) and their dimethyl esters (in CDCl₃ and CD₃OD) were established by means of NMR basing on the dependence between observed values of coupling constants (³J_HH, ³J_PC, ³J_HP) and corresponding dihedral angles. Potentiometric and spectroscopic methods were used for the evaluation of the structure of the complexes of (1S,2S)-2-amino-1-hydroxy-alkylphosphonic acids with Zn(II) and Cu(II) ions in aqueous solutions.     

Stereoselective synthesis of (E)-trisubstituted alpha,beta-unsaturated amides and acids

Potassium alkoxides of N-acyl-oxazolidin-2-one-syn-aldols undergo stereoselective elimination reactions to afford a range of trisubstituted (E)-alpha,beta-unsaturated amides in >95% de, that may be subsequently converted into their corresponding (E)-alpha,beta-unsaturated acids or (E)-alpha,beta-unsaturated oxazolines in good yield. syn-Aldols derived from alpha,beta-unsaturated aldehydes gave their corresponding trisubstituted (E)-alpha,beta-unsaturated-amides with poorer levels of diastereocontrol, whilst there was a similar loss in (E)-selectivity during elimination of syn-aldols derived from chiral aldehydes. These elimination reactions proceed via rearrangement of the potassium alkoxide of the syn-aldol to a 1,3-oxazinane-2,4-dione enolate intermediate that subsequently eliminates carbon dioxide to afford a trisubstituted (E)-alpha,beta-unsaturated amide. The (E)-selectivity observed during the E1cB-type elimination step has been rationalised using a simple conformational model that employs a chair-like transition state to explain the observed stereocontrol.     

Complexation of [S,S,S]- and [R,S,R]-isomers of N-bis [2-(1,2-dicarboxyethoxy)ethyl] aspartic acid with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous solution

In a search for environmentally friendly metal chelating ligands for industrial applications, the protonation and complex formation equilibria of [S,S,S]- and [R,S,R]-isomers of N-bis[2-(1,2-dicarboxyethoxy)ethyl] aspartic acid (BCA6) with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous 0.1 M NaCl solution were studied at 25°C by potentiometric titration. The model for complexation and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions (M ⁿ⁺), stable ML ^n?6 complexes dominated complex formation for both isomers. Differences in complexation models were found for binuclear species.     

新型多氨-多酰氨配体和氨基酸的三元铜(Ⅱ)配合物(英)

合成3个多氨-多酰氨配体1，12-二((α-羟甲基)苯基)-2，5，8，11-四氮杂十二烷-1，12-二酮(L₁)，1，13-二((α-羟甲基)苯基)-2，5，9，12-四氮杂十三烷-1，13-二酮(L₂)，1，15-二((α-羟甲基)苯基)2，5，8，11，14-五氮杂十五烷-1，15-二酮（L₃）。利用pH滴定分别在5.0 ℃，15.0 ℃，25.0 ℃，35.0 ℃测定了铜(Ⅱ)与这3种配体在     

Heteroleptic cobalt(II) and nickel(II) complexes with iminodiacetic and dicarboxylic acids in aqueous solution

Equilibria in binary and ternary systems containing cobalt(II) and nickel(II) salts, iminodiacetic acid, and dicarboxylates were studied by spectrophotometry at I = 0.1 (NaClO₄) and T = 20 ± 2°C. The molar and proton compositions of the resulting complexes and the pH ranges of their existence were determined. The stability constants of the homo- and heteroleptic complexes were calculated. The pH-distribution of the detected complexes was obtained. The experimental data were analyzed using the mathematical models that predict the existence of a wide spectrum of complex species in solution and allow ignoring those species that are negligible for accurate reproduction of the observed pattern.     

Stability of Copper(II), Nickel(II) and Zinc(II) Binary and Ternary Complexes of Histidine,Histamine and Glycine in Aqueous Solution

The binary and mixed-ligand complexes formed between ligands (histidine (His), histamine (Him) and glycine (Gly)) and some transition metals (Cu(II), Ni(II) and Zn(II)) were studied potentiometrically in aqueous solution at (25.0 ± 0.1) C and I = 0.10 M KCl in order to determine the protonation constants of the free ligands and stability constants of binary and ternary complexes. The complexation model for each system has been established by the software program BEST from the potentiometric data. The most probable binding mode for each binary species of histidine and for all mixed species was also discussed based upon derived equilibrium constants and stability constants related to the binary species. The ambidentate nature of the histidine ligand, i.e. the ability to coordinate histamine-like, imidazolepropionic acid-like and glycine-like modes was indicated from the results obtained. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters, log K, log X and ₁₁₁₀. The concentration distributions of various species formed in solution were also evaluated. In terms of the nature of metal ion, the complex stability follows the trend Cu(II) > Ni(II) > Zn(II), which is in agreement with the Irving-Williams order of metal ions. Thus, the results obtained were compared and evaluated with those in the literature.     

Thermodynamics of Ternary Complex Formation of Copper(II) and Nickel Iminodiacetates with Histidine in Solution

Calorimetric, potentiometric and spectrophotometric studies on the mixed–ligand complexes of copper(II) with nickel iminodiacetates (Ida) and histidine (His) have been carried out in aqueous solution at 298.15 K and ionic strength I = 0.5 mol·dm^?3 (KNO₃). The thermodynamic parameters of formation of various mixed complexes have been determined. The probable coordination modes of the complexone and histidine residues in the mixed ligand complexes are discussed.