Reacciones de compuestos organometálicos de Pt(IV) mononucleares y de Rh (II)dinucleares. Aspectos cinéticos y termodinámicos.

Abstract

This document presents the experimental work realised by Julio Esteban Moreno. It can be grouped in two different parts, Pt (IV) compounds chemistry (Chapter I) and dinuclear Rh (II) compounds chemistry (Chapter II-V). In the first case, the substitution reactions of a series of S, N and P_based ligand on cyclometallated Pt(IV) compounds has been studied as a function of entering and leaving ligands, temperature and solvent. For the second kind of compounds, kineticmechanistic studies of isomerization processes have been carried out (Chapter IV-V) and the determination of the equilibrium constants of the acid-base reaction of binuclear Rh(II) compounds with different Lewis bases has also been report (Chapter II). The versatility of the ligands in these compounds allows control of the activity and enantioselectivity of the catalysts. Steric and electronic properties can be modified by exchanging the bridging carboxylates and/or the metalated phosphines. For another point of view, it has been also interesting to study by X-Ray techniques this kind of compounds (Chapter III). The inherent backbone chirality of these binuclear compounds has been used for enantioselective reactions, as the racemic mixture can be separated by standard chromatographic methods. Even though, a new binuclear Rh(II) compound is obtained enantiomerically pure by slow evaporation of the solvent.