Organometallic-like C−H Bond Activation and C−S Bond Formation on the Disulfide Bridge in the RuSSRu Core Complexes

Abstract

C−S bond formations on the disulfide bridge in the dinuclear Ru^III complexes have been found in the reaction with unsaturated organic molecules, such as alkenes and ketones. The reactions are initiated by the organometallic-like C−H bond activation. Through the mechanistic study of these novel reactions, the specific nature of the disulfide bridging ligand has been unveiled: (i) the double bond character of the sulfur−sulfur bond, which allows the Diels−Alder-type [4 + 2] cycloaddition reaction with butadiene to form a C₄S₂ ring, (ii) the C−H bond activation on the S−S bond forming a C−S bond. All of the C−H activation reactions and the ensuing C−S bond formation reactions suggest that the disulfide ligand can act in a manner similar to the transition metal centers of the organometallic complexes.