Bifunctional metal/acid catalysis synthesis

Isomorphous substitution of T element in a molecular sieve material is very interesting in order to modify its acidic or redox catalytic and shape selective properties. Different ways to perform such a substitution are now well established either during synthesis or post synthesis in( luding solid-solid reaction between the zeolite and another oxide. The substituted eliiment may be strongly or weakly bound to the framework i.e. may remain stable or may give rise to well dispersed metallic oxide particles entrapped in the cavities. This results in different catalytic properties and may even lead to bifunctional catalysis as for Ga-ZSM-5 material. 

The cobalt(III)-promoted hydrolysis of amino acid esters and peptides and the application of cobalt(III) complexes to the synthesis of small peptides has been reviewed. The ability of a metal ion to cooperate with various inter- and intramolecular acids and bases and promote amide hydrolysis has been investigated. The cobalt complexes (5-10) were prepared as potential substrates for amide hydrolysis. Phenolic and carboxylic functional groups were placed within the vicinity of cobalt(III) chelated amides, to provide models for zinc-containing peptidases such as carboxypeplidase A. The incorporation of a phenol group as in (5) and (6) enhanced the rate of base hydrolysis of the amide function by a factor of 10 -fold above that due to the metal alone. Intramolecular catalysis by the carboxyl group in the complexes (5) and (8) was not observed. The results are interpreted in terms of a bifunctional mechanism for tetrahedral intermediate breakdown by phenol. 

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