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Activation of rac ‐Me 2 Si(ind) 2 ZrCl 2 by Methylalumoxane Modified by Aluminum Alkyls: An EPR Spin‐Probe, 1 H NMR, and Polymerization Study
Author(s) -
Bryliakov Konstantin P.,
Semikolenova Nina V.,
Panchenko Valenti.,
Zakharov Vladimir A.,
Brintzinger Hans H.,
Talsi Evgenii P.
Publication year - 2006
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200500443
Subject(s) - chemistry , electron paramagnetic resonance , adduct , alkyl , reagent , metallocene , lewis acids and bases , reactivity (psychology) , crystallography , ion , medicinal chemistry , stereochemistry , polymer chemistry , inorganic chemistry , polymerization , catalysis , organic chemistry , nuclear magnetic resonance , physics , polymer , medicine , alternative medicine , pathology
Summary: Solutions containing mixtures of methylalumoxane (MAO) and i Bu 3 Al give rise to 1 H NMR signals indicative of the presence of the mixed alkyl aluminum dimers i Bu 2 Al(µ‐Me) 2 Al i Bu 2 and of mixed clusters of the type (AlMe (1 + 2 x − y ) i Bu y O (1 − x ) ) n . These mixed clusters, as well as related species present in solutions containing either MAO–Et 3 Al or commercially available modified MAO (MMAO), appear to have stronger Lewis acidic sites and greater hydrodynamic radii than comparable clusters present in solutions of MAO alone, as judged from EPR signals observed in these solutions upon addition of TEMPO. When (SBI)ZrCl 2 (SBI = rac ‐Me 2 Si(ind) 2 ) is reacted with one of these mixed activator reagents, the mixed heterobinuclear cation [(SBI)Zr(µ‐Me) 2 AlMe i Bu] + appears to be formed, together with its methyl counterpart [(SBI)Zr(µ‐Me) 2 AlMe 2 ] + , which is normally predominant in the (SBI)ZrCl 2 /MAO system at [Al] MAO /[Zr] ratios above 100. In the presence of i Bu 3 Al, the formation of heterobinuclear cations is suppressed in favor of ion pairs containing the cation [(SBI)ZrMe] + in contact with a (MAO–TIBA)‐derived counter anion. The greater reactivity of these contact‐ion pairs, as compared to the normally prevalent AlMe 3 adducts, as well as an increased Lewis acidity of MMAO, and the ensuing decreased coordination ability of the [Me‐(MAO–TIBA)] − counter ion as compared to [Me‐MAO] − , are likely to contribute to the positive effects of TIBA additions on the co‐catalytic activity of MAO.