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.