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Synthesis and structural characterization of zirconium complexes supported by tridentate pyrrolide-imino ligands with pendant N-, O- and S-donor groups and their application in ethylene polymerization

Abstract : Zirconium complexes {L} ZrClx(THF)(n) [L = 2-(C4H3N-2'-CHQN) C2H4NHPh, x = 3, n = 1, 2a; L = 2-(C4H3N-2'-CHQN) C6H4-2-OPh, x = 3, n = 0, 2b; L = 2-(C4H3N-2'-CHQN) C6H4-2-SPh, x = 3, n = 1, 2c; L = 2-(C4H3N-2'-CHQN) CH2C6H4-2-OMe, x = 3, n = 0, 2d; L = 2-(C4H3N-2'-CHQN) C2H4NPh, x = 2, n = 0, 4a] were prepared and characterized by elemental analysis, NMR spectroscopy, and by X-ray crystallography for 2a and 4a. In the solid state, 2a and 4a are monomeric with the pyrrolide-imino-amine adopting a mer-configuration. Upon activation with methylaluminoxane (MAO), all Zr(IV) precatalysts were active in ethylene polymerization and exhibited high thermal stability operating effectively at 100 degrees C with activities up to 453 kg(PE) mol[Zr](-1) h(-1). The high-density polyethylenes produced are strictly linear with melting temperatures in the range of 134-136 degrees C, and crystallinities varying from 56% to 70%.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01709533
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Submitted on : Thursday, April 26, 2018 - 3:28:39 PM
Last modification on : Thursday, March 5, 2020 - 2:06:31 PM
Long-term archiving on: : Tuesday, September 25, 2018 - 3:16:50 AM

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A. C. Pinheiro, S. M. da Silva, Thierry Roisnel, Evgeni Kirillov, Jean-François Carpentier, et al.. Synthesis and structural characterization of zirconium complexes supported by tridentate pyrrolide-imino ligands with pendant N-, O- and S-donor groups and their application in ethylene polymerization. New Journal of Chemistry, Royal Society of Chemistry, 2018, 42 (2), pp.1477-1483. ⟨10.1039/c7nj04074a⟩. ⟨hal-01709533⟩

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