Coordinated water molecules

In an aquo-complex, loss of protons from the coordinated water molecules can occur, as with hydrated non-transition metal ions (p. 45). To prevent proton loss by aquo complexes, therefore, acid must usually be added. It is for these conditions that redox potentials in Chapter 4 are usually quoted. Thus, in acid solutions, we have... 

Recently Desimoni et used the same bis(oxazoline) ligand in the magnesium(II) catalysed Diels-Alder reaction of the N-acyloxazolidinone depicted in Scheme 3.4. In dichloromethane a modest preference was observed for the formation of the S-enantiomer. Interestingly, upon addition of two equivalents of water, the R-enantiomer was obtained in excess. This remarkable observation was interpreted in terms of a change from tetrahedral to octahedral coordination upon the introduction of the strongly coordinating water molecules. 

Hydroxyl Compounds. The aqueous chemistry of zirconium is complex, and in the past its understanding was compHcated by differing interpretations. In a study of zirconium oxide chloride and zirconium oxide bromide, the polymeric cation [Zr4(OH)g (H20)jg was identified (189) the earlier postulated moiety [Zr=0] was discarded. In the tetramer, the zirconium atoms are coimected by double hydroxyl bridges (shown without the coordinating water molecules) ... 

H20)4].3H20 is 10-coordinate and its stmcture is probably best regarded as being based on the same structure but with an extra water squeezed between the three coordinated water molecules. 

The thermodynamic stability of a species is a measure of the extent to which this species will be formed from other species under certain conditions, provided that the system is allowed to reach equilibrium. Consider a metal ion M in solution together with a monodentate ligand L, then the system may be described by the following stepwise equilibria, in which, for convenience, coordinated water molecules are not shown ... 

One important difference between the present and the previous case should be noted. For the hydroquinone clathrates, where the wall of a cavity consists of 12 OH groups, 6 adjacent carbon atoms, and 6 CH groups in ortho position to the OH groups, it seemed best to consider the product z qjk) as one unknown. For hydrates one may not do this the walls of both types of cavities consist exclusively of tetrahedrally-coordinated water molecules. Hence, one should use the same value of (,eg/k) —characteristic for a water molecule in a hydrate lattice—for both types of cavities and multi-... 

Some species have a large number of exchangeable hydrogens. Thus, metal ions with many coordinated water molecules will become completely deuterated in D20. For example, Co(H20) + becomes Co(D20) +. If there were a 2 percent secondary kie per bond, it would be amplified to (1.02)12 or 1.27. It would not be a simple matter to demonstrate the operation of a primary kie in such a system because of this, given the p/f difference between the two metal ions and the general effects of the solvent change. 

This is indeed observed and, particularly in higher oxidation states, coordinated water molecules are relatively acidic (Table 9-5). Water coordinated to an iron(iii) center is a stronger acid than acetic acid ... 

ESR spectra (Table 1). The JV-cyclohexylthiosemicarbazone, 13, complex formed the expected [Fe(13-H)2] with FeCl as the counterion [141]. However, [Fe(13) (13-H)H20]C104 was isolated from ethanol. Bulkiness of the cyclohexyl group, and the perchlorate ion s greater ability to hydrogen bond are probably both important to the stability of this cation. The iron(III) center is considered six-coordinate with a tridentate 13-H, bidentate 13, and a coordinated water molecule. 

Rate constant for the exchange of a particular coordinated water molecule. b RRSS form of macrocycle. c Five-coordinate RSRS form of macrocycle. d The two inequivalent H20 exchange at different rates. 

Where kf is the rate constant for the exchange of an unspecified one of the four coordinated water molecules recalculated to second-order units [ is the first-order rate constant (s 1) for the exchange of a particular coordinated solvent molecule]. 

Rate constant for the exchange of a particular coordinated water molecule. 

The matrix metalloprotease (MMP) family of zinc hydrolases are thought to play important roles in extracellular tissue remodeling in angiogenesis and other normal physiological processes, in some inflammatory processes and in metastatic processes in cancer. Like the zinc carboxypeptidases, the MMPs also utilize a zinc-coordinated water molecule to initiate attack on the scissile amide bond of protein substrates. These enzymes are synthesized by the ribosome in a latent form composed of a catalytic domain and an N-terminal extension, referred to as the prodomain the latent, or inactive form of the enzyme is referred to as a zymogen or... 

In the case of the rhenium aqua-ion [Re(OH2)3(CO)3]+ (33b) the question has been posed whether complex-anion can be considered to be a Bronsted acid. Titrations with hydroxide in water yielded a pKa value of 7.55 which is exceptionally low for a +1 cation. After the deprotonation of one coordinated water molecule, polymer formation over (/r-OH) bridges was initiated and the two compounds [Re3(/T3-OH)(/T-OH)3(CO)9r (35) and [Re2(/i-OH)3(CO)6] were (36) isolated and structurally characterized (Scheme 6). 

A strong decrease in relaxivity (from 12.8mM-1s-1 to 2mM-1s-1) between pH 6 and 11 has been reported for a positively charged macrocyclic Gdm complex (Scheme 10), which was explained by the successive deprotonation of the coordinated water molecules.167 Luminescence lifetime measurements of a Yb111 analogue proved that the complex possesses three bound waters at pH 5.5. Above pH 11, a di-oxo-bridged dimer is formed that has no more bound water or OH groups. 

Di or trivalent cations are able to induce the dissociation of coordinated water molecules to produce acidic species such as MOH+ (or MOH2+ for trivalent metal cations) and H+. Several infrared studies concerning rare-earth or alkali-earth metal cation exchanged Y zeolites have demonstrated the existence of such species (MOH+ or MOH2+) [3, 4, 5, 6]. However, the literature is relatively poor concerning the IR characterization of these acidic sites for LTA zeolites. The aim of the present work is to characterize 5A zeolite acidity by different techniques and adsorption tests carried on 5A zeolite samples with different ion exchange. 

---