Proton donation

Boron trioxide is not particularly soluble in water but it slowly dissolves to form both dioxo(HB02)(meta) and trioxo(H3B03) (ortho) boric acids. It is a dimorphous oxide and exists as either a glassy or a crystalline solid. Boron trioxide is an acidic oxide and combines with metal oxides and hydroxides to form borates, some of which have characteristic colours—a fact utilised in analysis as the "borax bead test , cf alumina p. 150. Boric acid. H3BO3. properly called trioxoboric acid, may be prepared by adding excess hydrochloric or sulphuric acid to a hot saturated solution of borax, sodium heptaoxotetraborate, Na2B407, when the only moderately soluble boric acid separates as white flaky crystals on cooling. Boric acid is a very weak monobasic acid it is, in fact, a Lewis acid since its acidity is due to an initial acceptance of a lone pair of electrons from water rather than direct proton donation as in the case of Lowry-Bronsted acids, i.e. 

A similar frequency shift is observed for their overtones or combination bands (204). It was also established that the proton-donating ability of the thiazole CH groups decreases in the order, 2>5>4 (204). 

Individual ammo acids differ m their acid-base properties This is important m peptides and proteins where the properties of the substance depend on its ammo acid constituents especially on the nature of the side chains It is also important m analyses m which a complex mixture of ammo acids is separated into its components by taking advantage of the differences m their proton donating and accepting power... 

THE EFFECT OF PROTON-DONATING MODEFIER ON THE SOLUBILITY ENHANCEMENT OF TRIS(p-DIKETONATO) CHROMIUM(HI) IN SUPERCRITICAL CARBON DIOXIDE... 

Low-temperature adsorption of weak CH proton-donating molecules such as CHFj, acetylene and its derivatives or HCN, enables one to chai acterize the basicity of surface electron-donating sites. 

Many organic reactions involve acid concentrations considerably higher than can be accurately measured on the pH scale, which applies to relatively dilute aqueous solutions. It is not difficult to prepare solutions in which the formal proton concentration is 10 M or more, but these formal concentrations are not a suitable measure of the activity of protons in such solutions. For this reason, it has been necessaiy to develop acidity functions to measure the proton-donating strength of concentrated acidic solutions. The activity of the hydrogen ion (solvated proton) can be related to the extent of protonation of a series of bases by the equilibrium expression for the protonation reaction. 

Anti stereochemistry can be explained by a mechanism in which the alkene interacts simultaneously with the proton-donating hydrogen halide and with a source of halide ion, either a second molecule of hydrogen halide or a free halide ion. The anti stereochemistry is consistent with the expectation that the attack of halide ion would be from the opposite... 

The Bamford-Stevens decomposition of tosylhydrazones by base has been applied to steroids, although not extensively. It has been demonstrated that the reaction proceeds via a diazo compound which undergoes rapid decomposition. The course of this decomposition depends upon the conditions in proton-donating solvents the reaction has the characteristics of a process involving carbonium ions, and olefins are formed, often accompanied by Wagner-Meerwein-type rearrangement. In aprotic solvents the diazo compound appears to give carbene intermediates which form olefins and insertion products ... 

Most steroid reactions of this type have been carried out in proton-donating solvents (see ref. 313 for an exception) and rearrangement is a common occurrence... 

Orthoboric acid, B(OH)3, is the normal end product of hydrolysis of most boron compounds and is usually made ( 160 000 tonnes pa) by acidification of aqueous solutions of borax. Price depends on quality, being 805 per tonne for technical grade and about twice that for refined material (1990). It forms flaky, white, transparent crystals in which a planar array of BO3 units is joined by unsymmetrical H bonds as shown in Fig. 6.25. In contrast to the short O—H O distance of 272 pm within the plane, the distance between consecutive layers in the ciystal is 318 pm, thus accounting for the pronounced basal cleavage of the waxy, plate-like ciystals, and their low density (1.48 g cm ). B(OH)3 is a very weak monobasic acid and acts exclusively by hydroxyl-ion acceptance rather than proton donation ... 

The criterion which has been extensively employed to distinguish A-l mechanisms from A-2 or A-SE2 mechanism has been the linearity of plots of reaction rate coefficient versus the acidity function h0. The acidity function (see Volume 2, p. 358) is a measure of the proton-donating ability of a medium (as measured by its tendency to protonate a base B) which is given by equation (11), viz. 

The proton-donating strength of an acid is measured by its acidity constant the proton-accepting strength of a base is measured by its basicity constant. The smaller the constants, the weaker the respective strengths. The larger the value of pK, the weaker the acid or base. 

When a solute is added to an acidic solvent it may become protonated by the solvent. If the solvent is water and the concentration of solute is not very great, then the pH of the solution is a good measure of the proton-donating ability of the solvent. Unfortunately, this is no longer true in concentrated solutions because activity coefficients are no longer unity. A measurement of solvent acidity is needed that works in concentrated solutions and applies to mixed solvents as well. The Hammett acidity function is a measurement that is used for acidic solvents of high dielectric constant. For any solvent, including mixtures of solvents (but the proportions of the mixture must be specified), a value Hq is defined as... 

Homocitrate is bound to the molybdenum atom by its 2-carboxy and 2-hydroxy groups and projects down from the molybdenum atom of the cofactor toward the P clusters. This end of FeMoco is surrounded by several water molecules (5, 7), which has led to the suggestion that homocitrate might be involved in proton donation to the active site for substrate reduction. In contrast, the cysteine-ligated end of FeMoco is virtually anhydrous. 

Then, substitution of the sulfur atom of Cys with an oxygen would greatly decrease the rate of reaction, because nucleophilicity, anion-stabilizing effect and proton-donating ability of OH group are far smaller than that of an SH group. 

The tertiary structure of glutamate racemase has already been resolved and it has also been shown that a substrate analog glutamine binds between two cysteine residues. These data enabled us to predict that the new proton-donating amino acid residue should be introduced at position 74 instead of Gly for the inversion of enantioselectivity of the decarboxylation reaction. 

If the proton-donating ability of the amino acid at 188 is weaker, then the enantioselectivity of the reaction will be reversed compared to that of native enzyme. As shown in Table 3, the absolute configuration of the products by this mutant is opposite to those of the products obtained by the native enzyme and the ee of the products dramatically increased to 94 and 96%, respectively. This inversion of the enantioselectivity of the reaction supports the reaction mechanism that the Cys 188 of the native enzyme is working as the proton donor to the intermediate enolate form of the product. ... 

Of greatest interest among the protic solvents are liquid ammonia (where solutions with a very low freezing point can be prepared) and anhydrous (glacial) acetic acid (which has a high proton-donating power). 

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