Ternary Complexes in Solution, XXX Increased Stability Through Intramolecular Stacking in Mixed-Ligand Cu 2+ and Zn 2+ Complexes of 2,2′ -Bipyridyl and Carboxymethyl Aryl Derivatives

1979 ◽  
Vol 34 (2) ◽  
pp. 208-216 ◽  
Author(s):  
Etelka Farkas ◽  
Beda E. Fischer ◽  
Rolf Griesser ◽  
Volker M. Rheinberger ◽  
Helmut Sigel
Keyword(s):  
Metal Ion ◽  
Ternary Systems ◽  
Ternary Complexes ◽  
Mixed Ligand ◽  
Difference Spectra ◽  
Ternary Metal ◽  
The Stability ◽  
Stability Enhancement ◽  
Aryl Sulfide ◽  
Enhanced Stability

Abstract The stability constants of ternary Cu 2+ and Zn 2+ complexes, each of which contains 2,2′-bipyridyl and a carboxymethyl aryl sulfide, were determined in 50% aqueous dioxane. A comparison of the stability of these ternary complexes with those formed with simple carboxylates demonstrates an enhanced stability of the carboxymethyl aryl sulfide containing mixed ligand complexes. This enhanced stability is not due to a thioether-metal ion interaction, but due to an intramolecular aromatic stacking interaction between the aryl moiety of the carboxymethyl aryl sulfide and 2,2′-bipyridyl. Indeed, by UV difference spectra and by PMR measurements it is possible to show that a binary (metal ion-free) stacked adduct between the aromatic moieties of the two mentioned ligands is formed. Furthermore, by studying the binary and ternary systems of Zn 2+ or Cu 2+ , 2,2′-bipyridyl and hydrocinnamate, i.e. 3-phenylpropionate (-S-of carboxymethyl phenyl sulfide is replaced by -CH2-), it becomes obvious that the thioether moiety is not essential for the observation of an enhanced stability of the ternary complexes. PMR shift studies of 2,2′-bipyridyl/Zn 2+ /carboxymethyl aryl sulfide systems confirm the presence of stacking in the corresponding ternary complexes. Depending on the kind of the ternary metal ion complex the stability enhancement, due to the intramolecular stacking between the aromatic parts of the coordinated ligands, is between about 0.2 to 0.5 log unit.

Ternary Complexes in Solution, XII. Models for Biological Mixed-Ligand Complexes: 2,2′-Bipyridyl-Cu2+-Oligoglycine Systems

1972 ◽  
Vol 27 (4) ◽  
pp. 353-364 ◽  
Author(s):  
Helmut Sigel ◽  
Rolf Griesser ◽  
Bernhard Prijs
Keyword(s):  
Coordination Sphere ◽  
Ternary Complexes ◽  
Mixed Ligand ◽  
Amide Group ◽  
Amide Proton ◽  
Mixed Ligand Complexes ◽  
Apical Position ◽  
Binary Complexes ◽  
The Stability ◽  
Ph Range

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.

scholarly journals Ternary Copper(II) Complexes in Solution[1,2] Formed With 8-Aza Derivatives of the Antiviral Nucleotide Analogue 9-[2-(Phosphonomethoxy)Ethyl]Adenine (PMEA)

2000 ◽  
Vol 7 (6) ◽  
pp. 313-324 ◽  
Author(s):  
Raquel B. Gómez-Coca ◽  
Larisa E. Kapinos ◽  
Antonín Holý ◽  
Rosario A. Vilaplana ◽  
Francisco González-Vílchez ◽  
...  
Keyword(s):  
Metal Ion ◽  
Biological Properties ◽  
Mixed Ligand ◽  
Aromatic Rings ◽  
Group 14 ◽  
Phosphonate Group ◽  
Nucleotide Analogue ◽  
Ether Oxygen ◽  
The Stability ◽  
Derivatives Of

The stability constants of the mixed-ligand complexes formed between Cu(Arm)2+, where Arm= 2,2'-bipyridine (Bpy) or 1,10-phenanthroline (Phen), and the dianions of 9-[2-(phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA) and 8-[2-(phosphonomethoxy)ethyl]-8-azaadenine (8,8aPMEA) (both also abbreviated as PA2-) were determined by potentiometric pH titrations in aqueous solution (25 °C; I = 0.1 M, NaNO3). All four ternary Cu(Arm)(PA) complexes are considerably more stable than corresponding Cu(Arm)(R-PO3) species, where R-PO32− represents a phosph(on)ate ligand with a group R that is unable to participate in any kind of interaction within the complexes. The increased stability is attributed to intramolecular stack formation in the Cu(Arm)(PA) complexes and also to the formation of 5-membered chelates involving the ether oxygen present in the -CH2-O-CH2-PO32− residue of the azaPMEAs. A quantitative analysis of the intramolecular equilibria involving three structurally different Cu(Arm)(PA) species is carried out. For example, about 5% of the Cu(Bpy)(8,8aPMEA) system exist with the metal ion solely coordinated to the phosphonate group, 14% as a 5-membered chelate involving the -CH2-O-CH2-PO32−residue, and 81% with an intramolecular stack between the 8-azapurine moiety and the aromatic rings of Bpy. The results for the other systems are similar though with Phen a formation degree of about 90% for the intramolecular stack is reached. The existence of the stacked species is also proven by spectrophotometric measurements. In addition, the Cu(Arm)(PA) complexes may be protonated, leading to Cu(Arm)(H;PA)+ species for which it is concluded that the proton is located at the phosphonate group and that the complexes are mainly formed by a stacking adduct between Cu(Arm)2+ and H(PA)-. Conclusions regarding the biological properties of these azaPMEAs are shortly indicated.

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