Solvation sphere, hydrogen bonding

Bjerrum s theory includes approximations that are not fully justified the ions are considered to be spheres, the dielectric constant in the vicinity of the ion is considered to be equal to that in the pure solvent, the possibility of interactions between ions other than pair formation (e.g. the formation of hydrogen bonds) is neglected and the effect of ion solvation during formation of ion pairs is not considered (the effect of the solvation on ion-pair structure is illustrated in Fig. 1.7). 

In aqueous solution, a metal complex is enclosed by several solvation spheres involving many solvent molecules. As recently shown, for mechanistic studies a reduced coordination sphere is sufficient (157,159), and therefore here inclusion of a third solvent molecule is sufficient. Addition of a third water molecule results in the exothermic formation of [Be(H20)2(L)--H20] and [Be(H20)2(LH)--H20]+, where the third hydrogen-bonded... 

In the course of our investigations to develop new chiral catalysts and catalytic asymmetric reactions in water, we focused on several elements whose salts are stable and behave as Lewis acids in water. In addition to the findings of the stability and activity of Lewis adds in water related to hydration constants and exchange rate constants for substitution of inner-sphere water ligands of elements (cations) (see above), it was expected that undesired achiral side reactions would be suppressed in aqueous media and that desired enanti-oselective reactions would be accelerated in the presence of water. Moreover, besides metal chelations, other factors such as hydrogen bonds, specific solvation, and hydrophobic interactions are anticipated to increase enantioselectivities in such media. 

Adsorption of Ag on the surface of PdO is also an interesting option offered by colloidal oxide synthesis. Silver is a well-known promoter for the improvement of catalytic properties, primarily selectivity, in various reactions such as hydrogenation of polyunsaturated compounds." The more stable oxidation state of silver is -F1 Aquo soluble precursors are silver nitrate (halide precursors are aU insoluble), and some organics such as acetate or oxalate with limited solubility may also be used." Ag" " is a d ° ion and can easily form linear AgL2 type complexes according to crystal field theory. Nevertheless, even for a concentrated solution of AgNOs, Ag+ does not form aquo complexes." Although a solvation sphere surrounds the cation, no metal-water chemical bonds have been observed. 

Similar measurements have given values for the fractionation factor of hydrogen-bonded complexes of the fluoride ion (Emsley et al., 1986c) and the acetate ion (Clark et al., 1988a) in acetic acid solution, [20] and [21]. For the chloride ion in acetic acid, the result (Emsley et al., 1986c) was cp = 1.26, which means that the exchangeable sites in acetic acid molecules in the solvation sphere of the chloride ion are favoured by deuterium compared to the sites in the bulk solvent. 

The attentive reader will realize that we have strayed rather far from the hard spheres of the Einstein theory to find applications for it. It should also be appreciated, however, that the molecules we are discussing are proteins that-through disulfide bridges and hydrogen bonding —have fairly rigid structures. Therefore the application of the theory —amended to allow for solvation and ellipticity —is justified. This would not be the case for synthetic polymers, which are best described as random coils and for which a different formalism is employed. This is the topic of Section 4.9. 

In aqueous solution the exchange process H20 + D20 2HD0 occurs very rapidly via proton transfer. Consequently, in H20—D20 mixtures the rare earth has an average number of O—H bonds in its solvation sphere, the number being proportional to the H20/D20 ratio. The major quenching of a rare-earth ion in solution is due to the hydrogen vibrations about it and is proportional to the number of these bonds. 

Figure 3 Overview of the receptor-ligand binding process. All species involved are solvated by water (symbolized by gray spheres). The binding free energy difference between the bound and unbound state is a sum of enthalpic components (breaking and formation of hydrogen bonds, formation of specific hydrophobic contacts), and entropic components (release of water from hydrophobic surfaces to solvent, loss of conformational mobility of receptor and ligand).

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