Mechanistic Studies in Ruthenium Chemistry

Abstract

The studies described in this thesis are predominantly concerned with the investigation of possible starting compounds of use in preparative ruthenium chemistry. Especially with those compounds which might lead conveniently to the formation of compounds of interest in mechanistic and photochemical studies. The synthesis of various Schiff base complexes of ruthenium (11) and (111) using the ligand N, N-ethylenebis (salicylideneimine) has been studied. Some complexes containing different unidentate ligands have been prepared and examined. The behaviour of bis(triphenyl-phosphine) -N, N-ethylenebis (salicylidenemiruntahetnoi) ruthenium (11) in alcohol or acetonitrile as solvent has been studied spectrophotometrically, as has the irradiation of bis(triphenylphosphine) N,N-ethylenebis (salicylideneiminato) ruthenium (11) in inert and air atmospher. The preparation of water soluble sulphonated phthalocyanine was attempted and the treatment of this water soluble ligand with different metal ions including ruthenium (11) examined. This time consuming topic has not been taken to its limits since it has proved impossible to obtain reliable analytical results, which are necessary for the characterization of products. The preparation of the ethanolic blue solution obtained by the reduction of ruthenium trichloride using hydrogen and Adams catalyst has been investigated. The rate of formation of the blue solution and the effect of temperature and various concentration of catalyst have been studied spectrophotomet_rically, and attempts made to utilize the solutions preparatively. Various procedures were attempted for the preparation of dichlorotetrakisdimethylsulphoxideruthenium (11) complexes as readily available intermediates. These are described as also are the results of kinetic and mechanistic studies on the claimed red isomer, which undergoes a siow isomerization in alcholic solution.