Superacid hydrates

The hydration of triple bonds is generally carried out with mercuric ion salts (often the sulfate or acetate) as catalysts. Mercuric oxide in the presence of an acid is also a common reagent. Since the addition follows Markovnikov s rule, only acetylene gives an aldehyde. All other triple-bond compounds give ketones (for a method of reversing the orientation for terminal alkynes, see 15-16). With allqmes of the form RC=CH methyl ketones are formed almost exclusively, but with RC=CR both possible products are usually obtained. The reaction can be conveniently carried out with a catalyst prepared by impregnating mercuric oxide onto Nafion-H (a superacidic perfluorinated resinsulfonic acid). ... 

Solid superacidic Nafion-H was also found to be effective in the hydration of acyclic alkenes.16 Isopropyl alcohol was produced with 97% selectivity in hydrating propylene17 at 150°C, whereas isobutylene yielded tert-butyl alcohol18 with 84% selectivity at 96°C. 

Some of these systems plus other equally acidic systems are described in this review. We may somewhat arbitrarily classify 100% H2SC>4 and other non-aqueous systems containing considerably more acidic species than the hydrated proton as superacid systems as their acidities are of a different order of magnitude from that encountered in the more familiar aqueous systems. 

It is generally admitted that skeletal transformations of hydrocarbons are catalyzed by protonic sites only. Indeed good correlations were obtained between the concentration of Bronsted acid sites and the rate of various reactions, e g. cumene dealkylation, xylene isomerization, toluene and ethylbenzene disproportionation and n-hexane cracking10 12 On the other hand, it was never demonstrated that isolated Lewis acid sites could be active for these reactions. However, it is well known that Lewis acid sites located in the vicinity of protonic sites can increase the strength (hence the activity) of these latter sites, this effect being comparable to the one observed in the formation of superacid solutions. Protonic sites are also active for non skeletal transformations of hydrocarbons e g. cis trans and double bond shift isomerization of alkenes and for many transformations of functional compounds e.g. rearrangement of functionalized saturated systems, of arenes, electrophilic substitution of arenes and heteroarenes (alkylation, acylation, nitration, etc ), hydration and dehydration etc. However, many of these transformations are more complex with simultaneously reactions on the acid and on the base sites of the solid... 

The addition of water causes the breakage of the coordination bonds to yield Bronsted acid sites strengthening Lewis acid sites, as shown in Scheme 17.4, for example. Many research groups report the simultaneous existence of Bronsted and Lewis acid sites or the reversible transformation between Bronsted and Lewis acidity upon hydration or dehydration [61, 106, 152]. Fraenkel suggests that in order to be an effective superacid, sulfated zirconia should contain a critical amount of moisture [155bj. Several workers propose that the strong acidity requires the presence of both Lewis and Br0nsted sites. 

Nafion (Figure 4.12), a perfluorinated polymer containing pendant sulfonic acid groups, is generally considered to be a solid superacid whose pK ranges from -5 to -9. It was earlier shown to be an active catalyst for various organic reacfions such as alkylation, isomerization, disproportionation, transalkylation, acylation, nitration, hydration, rearrangement, and so on. ° ° ... 

We will attempt to (a) tabulate the available measured and derived thermodynamic data for the protonation of important representative bases in aqueous acids, superacids, and the gas phase (b) show how these data may be used to estimate the ionization ratios of the different bases in aqueous acid media, including their pA"-values in water at 25° and at different temperatures (c) estimate the solvation energies of the onium ions of the protonated bases (d) relate the acidity function and hydration behavior of the different classes of bases in order to provide the necessary data for a practical theory of acidity functions. 

Many acid-catalyzed reactions can be advantageously carried out using solid superacids instead of conventional acid systems. The reactions can be carried out in either the gaseous or the liquid phase. Using the example Nafion-H (a perfluoroalkane resin sulfonic acid, developed by DuPont) solid acid, several simple procedures were reported to carry out alkylation, transbromination, nitration, acetalization, hydration, and so on. 

Both titania (anatase more than rutile) and, even more, zirconia (tetragonal more than monoclinic), when sulfated or covered with tungsten oxide become very active for some hydrocarbon conversion reactions such as -butane skeletal isomerization [263]. For this reason, a discussion began on whether these materials have to be considered superacidic. Spectroscopic studies showed that the sulfate ions [264] as well as the tungstate ions [265,266] on ionic oxides in dry conditions, are tetracoordinated with one short S=0 and W=0 bond (mono-oxo structure) as shown in Scheme 9.3(11). Polymeric forms of tungstate species could also be present [267]. However, in the presence of water the situation changes very much. According to the Lewis acidity of wolframyl species, it is believed that it can react with water and be converted in a hydrated form, as shown in Scheme 9.3. Residual... 

Besides the above reactions, any kind of acid-catalyzed reactions such as cracking of cumene, alkylation of benzene with propene, hydration of olefins, isomerization of cyclopropane, esterification of acetic acid with ethanol, etc. can be used for the estimation of the acidic property of solid acids. Skeletal isomerization of li-butane to -butane is used to check whether a solid acid has superacidity, since the isomerization is known not to be catalyzed even by 100% sulfuric acid. However, it should be noticed that the differentiation between acid strength and acid amount is not easy from the measurement of catalytic activity for an acid-catalyzed reaction. Characterization of acid catalysts by use of model reactions has been reviewed recently by Guisnet. ... 

There is a continuous search for new superacid catalysts. The kinetics of ROP of D3 and D4 initiated by protic borate complex (tetrakis(pentafluorophenyl)boric add hydrate), HB (C6Fs)4-3H2O, revealed that the reaction is first-order in monomer and first-order in initiator. The formation of cydic oligomers typical for CROP of cydosiloxanes initiated by protic acids was observed. 

Cycloisomerization of methyl-substituted 1,6-diene is also catalyzed by tin(rv) triflate (Equation (8.8)). DFT computations proposed that the mechanism does not involve the direct addition of the tin(IV) cation to a double bond because the catalyst regeneration step would be energetically unfeasible [24]. The active catalyst is a hydrated triflate salt where water molecule plays a decisive role to enable the smooth completion of the catalytic cycle. The diastereoselectivity observed in the cycloisomerization was associated with the transition-state geometries. DFT calculations also showed that protonation and deprotonation occur on a single face of the substrate. These considerations, correlated to the experiments, showed that Brpnsted superacids are not effective in Lewis superacid catalysis. 

A new type of catalyst, a cobalt carbonyl complex, has been found for low-temperature (viz. 50 °C) homogeneous hydroformylation of alkenes. Nafion-H (a superacidic perfluorinated resin sulphonic acid) impregnated with mercury is recommended as a catalyst for the hydration of alkynes R C=CR (R = H or aryl, R = H, alkyl, or aryl) to form ketones R CH2C0R. Two mild methods for the hydrolysis of vinyl halides to ketones have been described one utilizes Bp3,Et20 and mercury(ii) acetate in acetic acid and the second mercury(ii) acetate in trifluoroacetic acid/ ... 

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