Liquid phase reactions acid-base catalysis

Apart from acid-base catalysis, homogeneous catalysis occurs for other liquid-phase reactions. An example is the decomposition of H202 in aqueous solution catalyzed by iodide ion (II). The overall reaction is... 

The use of HPAs and multicomponenf polyoxometalates as catalysts in liquid-phase reactions was reviewed by Kozhevnikov. Moreover, an interesting minireview was published concerning the Friedel-Crafts acylation of arenes and the Fries rearrangement catalyzed by HPA-based solid acids. The results show that HPA-based solid acids, including bulk and supported heteropoly acids as well as heteropoly acid salts, are efficient and environmentally friendly catalysis for all reacfions analyzed. 

So far, the Polanyi relation has been applied only to catalytic sequences with free radicals as intermediates. But its scope is much wider. Many organic reactions in the liquid phase proceed through ionic intermediates and arc catalyzed by acids and bases. Before the Polanyi relation is shown to correlate rate constants in acid-base catalysis, it will be put in an equivalent form by a series of self-explanatory steps. The temperature is assumed to be constant. 

In contrast to the areas of heterogeneous oxidation catalysis and solid acid catalysis, the use of solid base catalysis in liquid phase reactions has not met the same level of breakthrough. 

An excellent demonstration of the tunability of ionic liquids for catalysis is provided by an investigation of the dimerization of 1-butene (235). A Ni(cod)(hfacac) catalyst (Scheme 23) was evaluated for the selective dimerization of 1-butene after it was dissolved in various chloroaluminate ionic liquids. Earlier work on this reaction with the same catalyst in toluene led to the observations of low activity and difficult catalyst separation. In ionic liquids of varying acidity, little catalytic activity was found. However, a remarkable activity was achieved by adding a weak buffer base to an acidic ionic liquid. The reaction took place in a biphasic reaction mode with facile catalyst separation and catalyst recycling. A high selectivity to the dimer product was obtained because of a fast extraction of the Cg product from the ionic liquid phase, with the minimization of consecutive reaction to give trimers. Among a number of weak base buffers, a chinoline was chosen. The catalyst performance was compared with that in toluene. The catalyitc TOF at 90°C in toluene was... 

As far as catalysis is concerned it is already benefiting from new developments such as supercritical fluids, ionic liquids, sol-gel technology, solid phase reactions, parallel and combinatorial chemistry and some of these can be coupled to microwave irradiation. Already a number of very efficient organometallic (mainly iridimn based) catalysts have been produced although we are still some way from the acid, base situation where tritia-tion (or detritiation) rates can be estimated from a knowledge of acid-base strengths. 

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