Group 4 complexes derived from o-carborane: synthesis, structures and ethylene polymerization properties

Nine thermally stable complexes (η5-Cp*)[η5-(C5H4)CMe2CB10H10CR]MCl2 (R=H and Me) and (η5-Cp*)[η5; η1-(C5H4)CMe2(CB10H10C)]MCl have been prepared via metathesis reactions of Cp*MCl3 (M=Ti, Zr and Hf, Cp*=pentamethylcyclopentadienyl) with monolithium salts of (C5H5)CMe2(CB10H10CR) (R=H and Me) and with dilithium salt of (C5H5)CMe2(CB10H10CH), respectively. These compounds have been fully characterized by various spectroscopic methods and elemental analyses. All of the compounds except (η5-Cp*)[η5-(C5H4)CMe2CB10H10CMe]HfCl2 were additionally characterized by a single crystal X-ray diffraction study, establishing their monomeric bent metallocene structural feature with carborane acting as a substituent or an ancillary ligand. The titanium and zirconium complexes produce high-density polyethylenes with the activity range of about 103–104 g PE per mol of M bar h in the presence of modified methylaluminoxane cocatalyst.