Comparative Calorimetric and 1H N.M.R. Studies of the Interaction of Ag(I) With a Series of Mixed-Donor Macrocycles Incorporating Nitrogen, Oxygen and or Sulfur Donor Atoms

1988 ◽  
Vol 41 (9) ◽  
pp. 1347 ◽  
Author(s):  
D Baldwin ◽  
LF Lindoy ◽  
DP Graddon
Keyword(s):  
Stability Constants ◽  
Macrocyclic Ligands ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Ligand Ratio ◽  
Deuterated Derivative ◽  
Titration Data ◽  
Ligand Species ◽  
Metal Ligand ◽  
Sulfur Donor

The interaction of silver ion with a range of mixed-donor macrocyclic ligands incorporating nitrogen, oxygen and/or sulfur donors has been investigated. Complementary calorimetric and n.m.r. studies in acetonitrile (and its deuterated derivative) were used to investigate the nature of the equilibria present as the metal/ ligand ratio was varied. In all systems the formation of a 1 : 1 species was observed, with a 1:2 (metal/ ligand ) species also being formed in the presence of excess ligand in the majority of cases. Enthalpies of formation for the various complexes have been determined. Stepwise stability constants for the respective [ AgL ]+ + L ↔ [AgL2]+ equilibria have been estimated from the calorimetric titration data, and the factors promoting the formation of the 1:2 species are discussed. The studies confirm the enhanced affinity of AgI for thioether donors over ether donors.

Thermodynamics of metal-ligand bond formation. XII. Adducts of Monothio-β-diketone complexes with pyridine and bipyridine

1974 ◽  
Vol 27 (6) ◽  
pp. 1351 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Thermodynamic Data ◽  
Benzene Solution ◽  
Bond Formation ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data are reported for the addition of pyridine and bipyridine in benzene solution to monothio-β-diketone complexes, ML2, of nickel(11), copper(11), zinc(11) and mercury(11). NiL2 gives NiL2(py)2 and NiL(bpy); ZnL2 gives ZnL2(py) and ZnL2(bpy); in both cases the data show that bipyridine is bidentate. CuL2 gives CuL2 (py) and CuL2 (bpy), with almost equal enthalpies of formation, but the higher stability of CuL2(bpy) shows bipyridine is probably bidentate. HgL2 gives HgL2(py) and a reaction with bipyridine which shows that an extremely unstable adduct is formed. All data were obtained by calorimetric titration.

scholarly journals Thermodynamics of metal-ligand bond formation. VIII. Pyridine adducts of zinc(II) β-diketonates

1973 ◽  
Vol 26 (11) ◽  
pp. 2537 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Benzene Solution ◽  
Equilibrium Constants ◽  
Bond Formation ◽  
Formation Constants ◽  
Adduct Formation ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Experimental Conditions ◽  
Metal Ligand ◽  
Ligand Bond

Equilibrium constants and enthalpies in benzene solution are reported for the formation of 1 : 1-adducts of pyridine with four zinc(II) complexes of β-diketones, determined by calorimetric titration. Adduct formation constants at 30�C fall in the range 300-2000 and enthalpies of formation lie between -15 and - 34 kJ mol-1. Though the enthalpies of formation differ little from those of corresponding copper(II) complexes, the adducts are about a hundred times more stable. The pyridine adduct of bis(2,2,6,6-tetramethylheptane-3,5-dionato)zinc(II) is entropy-stabilized relative to those of other complexes. No evidence was obtained for the addition of a second molecule of pyridine under the experimental conditions used.

Thermodynamics of metal-ligand bond formation. VII. Pyridine adducts of nickel(II) salicylideneiminato complexes

1973 ◽  
Vol 26 (11) ◽  
pp. 2379 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Inductive Effect ◽  
Benzene Solution ◽  
Bond Formation ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Alkyl Complexes ◽  
Aryl Complexes ◽  
Entropy Effects ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data have been obtained by calorimetric titration in benzene solution at 30�C for the reaction: NiL2+2py = NiL2(py)2 for 16 different nickel(II) complexes of Schiff bases of salicylaldehyde, 5- chlorosalicylaldehyde, and 5-chloro-2-hydroxybenzophenone. It has also been possible to obtain data for the trimerization of bis(N-phenyl-5- chlorosalicylideneiminato)nickel(II), and for two of the complexes estimates have been obtained for the addition of base in two successive steps. ��� Pyridine adducts, NiL2(py)2, of N-aryl complexes have enthalpies of formation about -40 kJ mol-1, those of N-alkyl complexes about -60 kJ mol-1 and a small inductive effect can be observed due to chloro substitution, but variations in stabilities of the adducts arise mainly from entropy effects. In the two systems studied most of the enthalpy of adduct formation is associated with addition of the second molecule of base.

Influence of the chain length and metal : ligand ratio on the self-organization processes of Cu2+ complexes of [1 + 1] 1H-pyrazole azamacrocycles

2020 ◽  
Vol 49 (25) ◽  
pp. 8614-8624 ◽  
Author(s):  
Alberto Lopera ◽  
Ariadna Gil-Martínez ◽  
Javier Pitarch-Jarque ◽  
Begoña Verdejo ◽  
Salvador Blasco ◽  
...  
Keyword(s):  
Chain Length ◽  
The Self ◽  
Self Organization ◽  
Ligand Ratio ◽  
Chain Lengths ◽  
Metal Ligand

The great versatility of the pyrazole moiety combined with polyamines of different chain lengths gives rise to remarkable coordination features.

scholarly journals Potentiometric and spectrophotometric studies of the complexation of Schiff-base hydrazones containing the pyrimidine moiety

2003 ◽  
Vol 68 (10) ◽  
pp. 729-749 ◽  
Author(s):  
H.S. Seleem ◽  
B.A. El-Shetary ◽  
S.M.E. Khalil ◽  
M. Shebl
Keyword(s):  
Schiff Base ◽  
Ionic Strength ◽  
Thermodynamic Parameters ◽  
Stability Constants ◽  
Elemental Analysis ◽  
Mass Spectra ◽  
Dissociation Constants ◽  
The Stability ◽  
Pyrimidine Moiety ◽  
Metal Ligand

Three Schiff-base hydrazones (ONN ? donors) were prepared by condensation of 2-amino-4-hydrazino-6-methylpyrimidine with 2-hydroxyacetophenone 2-methoxybenzaldehyde and diacetyl to yield 2-OHAHP, 2-OMeBHPand DHP respectively. The structures of these ligands were elucidated by elemental analysis, UV, IR, 1H-NMR and mass spectra. The metal?ligand stability constants of Mn2+, Fe3+,Co2+,Ni2+,Cu2+, Zn2+,Cd2+,UO22+ and Th4+ chelates were determined potentiometrically in two different media (75%(v/v) dioxane?water and ethanol?water) at 283, 293, 303 and 313 K at an ionic strength of 0.05 M (KNO3). The thermodynamic parameters of the 1:1 and 1:2 complexes were evaluated and are discussed. The dissociation constants of 2-OHAHP, 2-OMeBHP and DHPligands and the stability constants of Co2+, Ni2 and Cu2+ with 2-OHAHP were determined spectrophotometrically in 75 % (v/v) dioxane?water.

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