Synthesis, APPI Mass-Spectrometric Characterization, and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes - Archive ouverte HAL Access content directly
Journal Articles Catalysts Year : 2018

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

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Gilles Schnee
  • Function : Author
  • PersonId : 1041309
Leslie Bitard
  • Function : Author
  • PersonId : 1041311
Aurelien Vantomme
  • Function : Author
  • PersonId : 1041312
Alexandre Welle
  • Function : Author
  • PersonId : 1041313
Jean-Michel Brusson
  • Function : Author
  • PersonId : 1041314
Pierre Giusti
  • Function : Author
  • PersonId : 1041315

Abstract

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu(2)Flu)(Cp)}(2) (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu(2)-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-tBu(2)Flu)(Cp)}MCl(2)l(2)(p-, R = Me (3a-Zr-2, 3a-Hf-2), R = H (3b-Zr-2); m-, R = Me (3c-Zr-2), 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 Photolonization (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 a greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.
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hal-01973913 , version 1 (17-07-2019)

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Gilles Schnee, Mathilde Farenc, Leslie Bitard, Aurelien Vantomme, Alexandre Welle, et al.. Synthesis, APPI Mass-Spectrometric Characterization, and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes. Catalysts, 2018, 8 (11), pp.558. ⟨10.3390/catal8110558⟩. ⟨hal-01973913⟩
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