A comprehensive study of complexation between potassium salts and
18-crown-6 in 14 different
solvents shows stability constant K increases by
>104 from water to pure methanol or to
propylene
carbonate (PC), with constants increasing in the order H2O
< HMPT < DMSO < DMF <
MeCHOHMe < MeCN < Me2CO < MeOH < PC. The
mostly calorimetrically determined
thermodynamic values of complexation between metal ion m and ligand l
(ΔG
ml, ΔH
ml,
ΔS
ml) are
compared with a large range of available solvent properties.
Linear correlations (with coefficients
R ≈ >0.95) are obtained for ΔG
ml
with standard Gibbs transfer energies ΔG°t
of the metal ion from
water to the given solvent. Analyses of literature data with some
other cations and ligands,
including the [222] cryptand, also revealed , that the complexation
constant changes are essentially
a linear function of the cation desolvation free energies. Less
meaningful correlations (R ≈ <0.9)
are obtained with values characterizing the electron donor capacity of
the solvent. Parameters
characterizing the solvent polarity, such as E
T,
are extremely poor descriptors (R = 0.3) of
the
medium effects. In binary dioxane−water mixtures
ΔG
ml and even ΔH
ml
correlates well with the
vol % of water, or with corresponding solvophobicity parameters
S
p (R = 0.97). The
reaction
enthalpies ΔH vary much more than ΔG, for
instance from 12 kJ/mol (in MeCN) to 68 kJ/mol (in
Me2CHOH), without meaningful correlations to known
solvent properties, or between ΔG and
ΔH.
An exception is the correlation of ΔH with the
solvent polarity index π* (with R = 0.996, if
MeCN
is excluded). Solvent effects on the ligands are studied by NMR in
view of the possible geometry
changes of crown ethers from oxygen-in (with aprotic solvents) to
oxygen-out (with water)
conformations of the macrocycles. Preliminary NMR results,
however, point to similar oxygen-in
conformations in water as well as in chloroform, in line with molecular
mechanics calculations.
complexes with K ؉ . Formation of poly-nuclear (M ؉ ) n L complexes of tri-podands in solution has been confirmed by electro-spray mass spectrometry. At relatively small concentrations of the ligand (C 0 L ), P1 binds Na ؉ much better than Li ؉ , whereas P4 and P5 display a remarkable Li ؉ /Na ؉ selectivity; at large C 0 L the complexation selectivity decreases. X-Ray diffraction studies performed on monocrystals of complexes of NaNCS with tri-podands P2 and P3 show that Na ؉ is encapsulated inside a 'basket-like' pseudocavity, coordinating all donor atoms of the tri-podand. Molecular dynamics simulations on P2, P3 and P4 and on their 1 : 1 complexes with M ؉ in acetonitrile solution suggest that the structures of M ؉ L complexes in solution are similar to those found for P2 and P3 complexes in the solid state.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.