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Zirconium Complexes of a Rigid, Dianionic Pincer Ligand: Alkyl Cations, Arene Coordination, and Ethylene Polymerization
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...
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Published in: | Organometallics 2017-08, Vol.36 (16), p.3084-3093 |
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Main Authors: | , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | 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 (M w) of 70,800–88,100 g mol–1 and polydispersities (M w/M n) of 3.94–4.67. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/acs.organomet.7b00424 |