ABSTRACT

Research in coordination and organometallic chemistry, strongly supported in the last decade by theoretical studies,1-13 has provided much insight into the mechanism of catalytic processes involving M-C or M-H bonds. Alkene metathesis is one example  of a cata lytic process involving M-C bonds that has been successfully applied in both academic and industrial environments with combined experimental and theoretical support.8,10,14 This resulted in the calculation of certain mechanistic parameters for the alkene metathesis mechanism with ruthenium carbenes.6,7,9,10,12,15-20 However, these studies focused on the catalytic cycle and ligand dissociation of the methylidene species RuCl2(PR3)2(=CH2) with model PR3 (R = H, Me) ligands and/or ethene as a model substrate to mainly reduce the computing cost. Therefore, the steric and electronic in§uence of the actual ligands [PCy3 vs. PR3, (R = H, Me)] and substrates (1-octene vs. ethene) with the benzylidene complex (vs. methylidene complex) as a precatalyst was not taken into consideration. Nonetheless, with the use of molecular modeling, a deeper insight was gained on the mechanism of the alkene metathesis reaction.