Catalytic Behavior of Half‐Metallocene Non‐Cp‐Type Group 4 Metal Complexes (M=Zr, Hf) with a Cyclooctatetraenyl Dianion during Olefin Polymerization

Abstract

AbstractSignificant advancements have been made in metallocene catalysis due to the development of cyclopentadienyl (Cp) ligands by numerous researchers. Furthermore, various ligand combinations have been realized in the last 20 years for the development of post‐metallocene catalysts. Although ligands containing a Cp have been widely reported, only a few reports exist ligands based on other carbon‐only π‐electron moieties. Herein, we focused on the zirconium and hafnium with the 10π‐electron cyclooctatetraenyl (Cot) dianion as an ancillary ligand and investigated the olefin‐polymerization ability of these complexes. Thus, we performed ethylene and ethylene‐1‐octene (co)polymerization using dMAO, MMAO, and Ph3C[B(C6F5)4]/iBu3Al as cocatalysts and confirmed that completion of the polymerization reaction; the catalytic system except dMAO exhibited activities for olefin polymerization to give linear polyethylene or ethylene‐1‐octene copolymer. Furthermore, the zirconium complexes bearing trimethylsilyl‐substituted Cot ligand exhibited enhanced activities for ethylene polymerization compared with an unsubstituted CotZr catalyst.