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Reactive Intermediates Formed During Olefin Polymerization by Methylalumoxane-Activated ansa-Zirconocene Catalysts: Identification of a Chain-Carrying Intermediate by NMR Methods
Author(s) -
Dmitrii E. Babushkin,
Hans H. Brintzinger
Publication year - 2009
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/ja909157r
Subject(s) - chemistry , allylic rearrangement , olefin polymerization , catalysis , olefin fiber , hexene , polymer chemistry , polymerization , chain (unit) , long chain , stereochemistry , medicinal chemistry , organic chemistry , ethylene , polymer science , polymer , physics , astronomy
Addition of 1-hexene to methylalumoxane-activated catalyst systems based on rac-Me(2)Si(ind)(2)ZrMe(2) causes, concurrent with polyhexene formation and diminution of the otherwise prevalent cation [rac-Me(2)Si(ind)(2)Zr(mu-Me)(2)AlMe(2)](+), formation of a hitherto unobserved species [rac-Me(2)Si(ind)(2)Zr(mu-R)(mu-Me)AlMe(2)](+), where R is a Zr-bound polyhexyl chain. As hexene is increasingly consumed, this cation decays, mainly back to [rac-Me(2)Si(ind)(2)Zr(mu-Me)(2)AlMe(2)](+) and, in part, to some species containing a Zr-bound allylic chain end.

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