RUTHENIUM-CATALYZED OLEFIN METATHESIS: APPLICATIONS IN GREEN AND SUSTAINABLE CHEMISTRY

THIS DOCTORAL THESIS FOCUSES ON THE PRIMARY OBJECTIVE OF DEVELOPING NEW HOVEYDA-GRUBBS TYPE RUTHENIUM CATALYSTS FOR OLEFIN METATHESIS FEATURING UNSYMMETRICAL N-BENZYL, N’-ARYL NHC FRAMEWORKS WITH SUBSTITUTED BACKBONES IN BOTH SYN AND ANTI CONFIGURATIONS. FOLLOWING THEIR SYNTHESIS, THESE NOVEL CATALYSTS WILL BE EVALUATED ACROSS A BROAD RANGE OF CATALYTIC APPLICATIONS INVOLVING STANDARD AND RENEWABLE SUBSTRATES, INCLUDING RING-CLOSING METATHESIS, CROSS METATHESIS, SELF-METATHESIS, ETHENOLYSIS AND RING-OPENING METATHESIS POLYMERIZATION. THE RESULTING PERFORMANCES WILL BE COMPARED WITH THOSE OF THE COMMERCIALLY AVAILABLE SYMMETRICAL HOVEYDA-GRUBBS SECOND GENERATION CATALYST (HGII) AND OTHER RELATED NHC CATALYSTS PREVIOUSLY REPORTED IN THE LITERATURE. OVERALL, THIS STUDY AIMS TO ELUCIDATE HOW SPECIFIC STRUCTURAL MODIFICATIONS TO NHC LIGANDS AFFECT CATALYST EFFICIENCY ACROSS DIVERSE METATHESIS TRANSFORMATIONS. AN ADDITIONAL AIM IS TO OPTIMIZE THE REACTION CONDITIONS FOR CROSS METATHESIS TO PROMOTE THE VALORIZATION OF WASTE-DERIVED Α-ALKENES OBTAINED FROM PLASTIC WASTE, PARTICULARLY POLYPROPYLENE AND POLYETHYLENE. THIS OPTIMIZATION PROCESS WILL INVOLVE SYSTEMATIC ADJUSTMENT OF REACTION PARAMETERS SUCH AS TEMPERATURE, CONCENTRATION, REACTION TIME, SOLVENT CHOICE, AND CATALYST ADDITION PROTOCOLS. FURTHERMORE, A COMPREHENSIVE INVESTIGATION OF THE SCOPE AND LIMITATIONS OF THE CROSS METATHESIS REACTION WILL BE CARRIED OUT USING A VARIETY OF CROSS-PARTNERS.