Aluminum- and gallium-bridged ansa-zirconocene compounds (Pytsi)Al[1]ZCP (31a) and (Pytsi)Ga[1]ZCP (31b) containing a bulky trisyl-based ligand with a pyridyl donor group [Pytsi = -C(SiMe3)2SiMe2(2-C5H4N)] were synthesized in 31% and 40% yield, respectively, by the reaction of (Pytsi)ECp2 [E = Al (29a), Ga (29b)] with Zr(NMe2)4 followed by reaction with Me3SiCl. Compounds 29a and 29b were prepared by the reaction of (Pytsi)ECl2 [E = Al (28a), E = Ga (28b)] with two equivalents of NaCp. The molecular structures of 29a and 29b were elucidated in solution by 1H and 13C NMR spectroscopy. Species 31a was characterized by multinuclear NMR spectroscopy while 31b was characterized by CHN elemental analysis, 1H and 13C NMR spectroscopy and mass spectrometry. Both species are the only known examples of aluminum- and gallium-bridged ansa-zirconocenes. Compound 31b in combination with MAO was applied and shown to be highly active for ethylene polymerization at room temperature. The activity of 31b was compared to that obtained for Cp2ZrCl2 using a glass reactor system and was found to be comparable. The influence of precatalyst concentration and ethylene pressure on activity of 31b was studied.

Aluminum- and gallium-bridged ansa-zirconocene compounds (Pytsi)Al[1]ZCP (31a) and (Pytsi)Ga[1]ZCP (31b) containing a bulky trisyl-based ligand with a pyridyl donor group [Pytsi = -C(SiMe3)2SiMe2(2-C5H4N)] were synthesized in 31% and 40% yield, respectively, by the reaction of (Pytsi)ECp2 [E = Al (29a), Ga (29b)] with Zr(NMe2)4 followed by reaction with Me3SiCl. Compounds 29a and 29b were prepared by the reaction of (Pytsi)ECl2 [E = Al (28a), E = Ga (28b)] with two equivalents of NaCp. The molecular structures of 29a and 29b were elucidated in solution by 1H and 13C NMR spectroscopy. Species 31a was characterized by multinuclear NMR spectroscopy while 31b was characterized by CHN elemental analysis, 1H and 13C NMR spectroscopy and mass spectrometry. Both species are the only known examples of aluminum- and gallium-bridged ansa-zirconocenes. Compound 31b in combination with MAO was applied and shown to be highly active for ethylene polymerization at room temperature. The activity of 31b was compared to that obtained for Cp2ZrCl2 using a glass reactor system and was found to be comparable. The influence of precatalyst concentration and ethylene pressure on activity of 31b was studied.