Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Synthesis, APPI Mass-Spectrometric Characterization and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes

Version 1 : Received: 25 October 2018 / Approved: 25 October 2018 / Online: 25 October 2018 (13:04:21 CEST)

A peer-reviewed article of this Preprint also exists.

Schnee, G.; Farenc, M.; Bitard, L.; Vantomme, A.; Welle, A.; Brusson, J.-M.; Afonso, C.; Giusti, P.; Carpentier, J.-F.; Kirillov, E. Synthesis, APPI Mass-Spectrometric Characterization, and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes. Catalysts 2018, 8, 558. Schnee, G.; Farenc, M.; Bitard, L.; Vantomme, A.; Welle, A.; Brusson, J.-M.; Afonso, C.; Giusti, P.; Carpentier, J.-F.; Kirillov, E. Synthesis, APPI Mass-Spectrometric Characterization, and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes. Catalysts 2018, 8, 558.

Abstract

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a‒c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2); m-, R = Me (3c-Zr2) were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

Keywords

metallocene catalysts; mass-spectroscopy; olefin polymerization

Subject

Chemistry and Materials Science, Inorganic and Nuclear Chemistry

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