Ternary complexes in solution. 41. Ternary complexes in solution as models for enzyme-metal ion-substrate complexes. Comparison of the coordination tendency of imidazole and ammonia toward the binary complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), or Cd(II) and uridine 5'-triphosphate or adenosine 5'-triphosphate

1982 ◽  
Vol 104 (15) ◽  
pp. 4100-4105 ◽  
Author(s):  
Nityananda Saha ◽  
Helmut Sigel
2012 ◽  
Vol 9 (4) ◽  
pp. 2394-2406 ◽  
Author(s):  
Anil B. Zade ◽  
Pawan P. Kalbende ◽  
Mayuri S. Umekar ◽  
Gajanan W. Belsare

Cetyldimethylethylammonium bromide, a cationic surfactant has been used to decolorize eriochromeazurol B, an anionic triphenylmethane type of dye. Addition of specific lanthanide metal ion to this decolorized solution resulted into intense colored stable ternary complex with large bathochromic shift from 540 nm (binary complex) to 650 nm (ternary complex) with increase in absorbance values at shifted wavelength. CDMEAB thus decreases the color intensity of ECAB and increases the absorbance value of ternary complexes. This two fold advantage resulted into enhancement in molar absorptivities and sensitivities at shifted wavelength of ternary complexes with stoichiometric composition 1:(1:3)2, [Ln : (R:S)] for all lanthanides understudy namely yttrium, neodymium, europium, terbium and ytterbium. The ternary complexes at pH 6.0 exhibited absorption maxima at 650 nm with molar absorptivities 69000 L.mol-1.cm-2for Y(III), 66000 L.mol-1.cm-2for Nd(III), 69000 L.mol-1.cm-2for Eu(III), 64000 L.mol-1.cm-2for Tb(III), 70000 L.mol-1.cm-2for Yb(III). Beer's law were obeyed in concentration range 0.11-0.94, 0.19-1.53, 0.2-1.41, 0.21-1.69 and 0.23-1.11 ppm for Y(III), Nd(III), Eu(III), Tb(III) and Yb(III) respectively. Conditional formation constants and various analytical parameters have been evaluated and compared the results of newly formed ternary complexes with binary complexes. Finally newly suggested modified method have been recommended for the microdetermination of lanthanides understudy.


1982 ◽  
Vol 47 (2) ◽  
pp. 503-508 ◽  
Author(s):  
Irena Němcová ◽  
Pavla Plocková ◽  
Tran Hong Con

The absorption spectra of the binary complexes of lanthanoids with bromopyrogallol red were measured and the formation of ternary complexes with cation active tenside, Septonex, was studied. Optimal conditions were found for the formation of these complexes and the possibility of their use in the photometric determination of lanthanoids was demonstrated on several examples.


1993 ◽  
Vol 58 (5) ◽  
pp. 1103-1108 ◽  
Author(s):  
Mohamed M. Shoukry ◽  
Eman M. Shoukry

The formation constants of the binary and ternary complexes of palladium(II) with diethylenetriamine and amino acids as ligands have been determined potentiometrically at 25 °C in 0.1 M NaNO3 solution. The relative stability of each ternary complex was compared with that of the corresponding binary complexes in terms of ∆logK values. The mode of chelation was ascertained by conductivity measurements.


2017 ◽  
Vol 203 ◽  
pp. 29-45 ◽  
Author(s):  
Janet E. Del Bene ◽  
Ibon Alkorta ◽  
José Elguero

Ab initio MP2/aug’-cc-pVTZ calculations have been carried out to determine the effect of the presence of one halogen bond on the nature of the other in ternary complexes H2XP:ClF:ClH and H2XP:ClF:ClF, for X = F, Cl, H, NC, and CN. The P⋯Cl bonds remain chlorine-shared halogen bonds in the ternary complexes H2XP:ClF:ClH, although the degree of chlorine sharing increases relative to the corresponding binary complexes. The F⋯Cl bonds in the ternary complexes remain traditional halogen bonds. The binding energies of the complexes H2XP:ClF:ClH increase relative to the corresponding binary complexes, and nonadditivities of binding energies are synergistic. In contrast, the presence of two halogen bonds in the ternary complexes H2XP:ClF:ClF has a dramatic effect on the nature of these bonds in the four most strongly bound complexes. In these, chlorine transfer occurs across the P⋯Cl halogen bond to produce complexes represented as (H2XP–Cl)+:−(F:ClF). In the ion-pair, the cation is also halogen bonded to the anion by a Cl⋯F− halogen bond, while the anion is stabilized by an −F⋯Cl halogen bond. The central ClF molecule no longer exists as a molecule. The binding energies of the ternary H2XP:ClF:ClF complexes are significantly greater than the binding energies of the H2XP:ClF:ClH complexes, and nonadditivities exhibit large synergistic effects. The Wiberg bond indexes for the complexes H2XP:ClF, H2XP:ClF:ClH, and H2XP:ClF:ClF, and the cations (H2XP–Cl)+ reflect the changes in the P–Cl and Cl–F bonds. Similarly, EOM-CCSD spin–spin coupling constants are also consistent with the changes in these same bonds. In particular, 1xJ(P–Cl) in H2XP:ClF complexes becomes 1J(P–Cl) in the ternary complexes with chlorine-transferred halogen bonds. A plot of these coupling constants shows a change in the curvature of the trendline as chlorine-shared halogen bonds in H2XP:ClF:ClH become chlorine-transferred halogen bonds in H2XP:ClF:ClF. 1xJ(F–Cl) coupling constants also reflect changes in the nature of F⋯Cl halogen bonds.


1972 ◽  
Vol 27 (4) ◽  
pp. 353-364 ◽  
Author(s):  
Helmut Sigel ◽  
Rolf Griesser ◽  
Bernhard Prijs

The stability constants of the binary Cu2+ complexes of glycine amide, diglycine, diglycine amide, triglycine, and tetraglycine were determined, as were those of the mixed-ligand Cu2+ systems containing 2,2′-bipyridyl and one of the mentioned oligoglycines. The results evidence that all these complexes have the same structure and, therefore, the binding sites of the ligands have to be the terminal amino group and the oxygen of the neighbored amide group. The stability differences between the ternary and the binary complexes are in agreement with this interpretation. It is of interest to note that these ternary complexes are significantly more stable than expected on statistical reasons. With increasing pH, the amide groups in the binary complexes are successively deprotonated. Thus, with tetraglycine finally all three amide protons are displaced, and the amide nitrogens are bound to the square-planar coordination sphere of Cu2+. As in the Cu2+-2,2′-bipyridyl 1 : 1 complex, only two coordination positions are left for the binding of the oligoglycine, in the tenary complexes, only one amide group can be deprotonated. An increase in pH with deprotonation of other amide groups leads to a displacement of 2,2′-bipyridyl, i. e. the simple binary complexes result. No evidence could be observed for the coordination of a deprotonated amide group to an apical position of the coordination sphere of Cu2+. Additionally, while the displacement of the first amide proton in the several binary Cu2+ oligoglycine complexes occurs over a large pH range (4 to 7), the deprotonation in all the mixed-ligand complexes takes place at pH approximately 8.


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