Intermetallic Cooperation in Olefin Polymerization Catalyzed by a Binuclear Samarocene Hydride: A Theoretical Study

The cooperative effect in bi- and multinuclear metal complexes is of great interest in catalysis since such a cooperative effect often gives the complexes unique catalytic performance unavailable in mononuclear analogues. However, the related mechanism of bi- and multinuclear cooperative catalysis remained almost unexplored. Herein, the detailed mechanism of ethylene polymerization by a binuclear samarocene hydride complex has been computationally modeled. The results have not only revealed new aspects of the mechanism of olefin insertion reactions but also provided theoretical evidence for electronic communication between the metal centers during the polymerization, where the bridging hydride ligand plays an important role in such an intermetallic cooperation.