3 years ago

Zirconium Complexes of a Rigid, Dianionic Pincer Ligand: Alkyl Cations, Arene Coordination, and Ethylene Polymerization

Zirconium Complexes of a Rigid, Dianionic Pincer Ligand: Alkyl Cations, Arene Coordination, and Ethylene Polymerization
Jeffrey S. Price, Hilary A. Jenkins, Kelly S. A. Motolko, David J. H. Emslie, James F. Britten
Reaction of 4,5-bis(2,4,6-triisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene (H2XN2) with [Zr(NMe2)4], followed by crystallization from O(SiMe3)2, yielded [(XN2)Zr(NMe2)2]·{O(SiMe3)2}0.5 (1·{O(SiMe3)2}0.5). The zirconium dimethyl complex [(XN2)ZrMe2] (2) was subsequently accessed (a) by treatment of 1·(O(SiMe3)2)0.5 with excess AlMe3 or (b) via reaction of 1·(O(SiMe3)2)0.5 with excess Me3SiCl, affording [(XN2)ZrCl2] (3) followed by reaction of 3 with 2 equiv of MeLi. Reaction of [(XN2)ZrMe2] (2) with one equiv of B(C6F5)3 or [CPh3][B(C6F5)4] yielded cationic [(XN2)ZrMe][MeB(C6F5)3] (4) and [(XN2)ZrMe(arene)][B(C6F5)4] {arene = η6-benzene (5a), η6-toluene (5b), or bromobenzene (5c)}, respectively. Both 4 and 5b are active for ethylene polymerization under 1 atm of ethylene at 24 and 80 °C in toluene with activities ranging from 23.5–883 kg mol–1 atm–1 h–1, yielding polymers with weight-average molecular weights (Mw) of 70,800–88,100 g mol–1 and polydispersities (Mw/Mn) of 3.94–4.67.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00424

DOI: 10.1021/acs.organomet.7b00424

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