Highly fluorous zirconocene(IV) complexes and their catalytic applications in the polymerization of ethylene

The catalytic activities of the highly fluorous systems formed by the zirconocene(IV) complexes [Zr{η5-C5H4SiMe2C2H4RF}2Cl2] (RF = C6F13 (4a), C10F21 (4b)) or [Zr-{η5-C5H3(SiMe2C2H4C6F13)2}2Cl2] (5a) and MMAO in toluene have been studied and compared with analogous nonfluorous systems generated from [Zr{η5-C5H4SiMe3}2Cl2] and [Zr{η5-C5H5}2Cl2]. Although less active than the reference systems, the fluorous catalysts are stable over prolonged polymerization times, giving rise to polymers with similar molecular weights to those obtained with [Zr{η5-C5H4SiMe3}2Cl2].