CENTRO DE INVESTIGACION Y DESARROLLO EN CIENCIAS APLICADAS "DR. JORGE J. RONCO"
Unidad Ejecutora - UE
capítulos de libros
Experimental and theoretical studies on chiral heterogeneous catalysts for hydrogenation reactions
JOSÉ F. RUGGERA; ANDREA B. MERLO; VIRGINIA VETERE; MÓNICA L. CASELLA
Electronic and Catalytic Properties of advanced Materials
Transworld Research Network
Lugar: Kerala; Año: 2011; p. 171 - 232
The preparation of pure chemical compounds has been one of the most rapid growing areas in chemistry over the last decades with heterogeneous catalysis being recognized as providing new possibilities. In this contribution, two different strategies are studied for obtain enantioselectivity through heterogeneous catalysis: the use of a chiral species to modify a solid surface and the grafting of a chiral organotin compound on a metallic catalyst (via Surface Organometallic Chemistry on Metals techniques, SOMC/M). Both types of systems are applied to enantioselective hydrogenation reactions. The hydrogenation of ethyl pyruvate was studied using (S)-(+)-1-aminoindan and (R)-(-)-1-aminoindan as chiral modifiers of a Pt/SiO2 catalyst, using two different solvents (toluene and acetic acid), in order to analyze their influence on the reaction. The approach employed to explain the experimental results, consisted of the molecular modeling of the transition states. In acetic acid, it was observed an inversion in the sense of the enantiomeric excess (ee %), which was corroborated by means of the molecular modeling of the transition complexes formed between modifier and substrate. The origin of the sense of the ee% seems to be given by the relative abundance of the chiral modifier/substrate complex.In the SOMC/M approximation, the modelization of organotin precursor compounds of general formula Men-Sn-R3 (R´ = achiral fragment) that could be employed for the obtention of enantioselective heterogeneous catalysts, was studied. To do so, molecular modelling, both at the level of Mechanics and Molecular Dynamics and Density Functional Theory (DFT), was used.