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Volumn 44, Issue 11, 2005, Pages 1668-1671

C3 chirality in polymerization catalysis: A highly active dicationic scandium(III) catalyst for the isoselective polymerization of 1-hexene

Author keywords

Homogeneous catalysis; Polymerization; Polymers; Scandium; Stereocontrol

Indexed keywords

CATALYSIS; MOLECULAR STRUCTURE; OLEFINS; STEREOCHEMISTRY;

EID: 17044371606     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200462804     Document Type: Article
Times cited : (141)

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    • note
    • The highest tacticity control is observed at +40°C while the tacticity is lower at ambient temperature and below, which is probably in part due to aggregation of the catalyst (and manifest in the bimodal GPC traces). This observation is only consistent with enantiomorphic tacticity control.
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    • 1H NMR spectra of all the polymer samples produced by the dicationic species, no signals attributable to olefinic end groups were observed to within the detection limits of the instrument. Therefore, although we cannot rule out β-hydride elimination altogether, it is certainly not a significant contributor.
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    • An additional control experiment to distinguish enantiomorphic from chain-end tacticity control would entail the use of an achiral trisox ligand. We previously reported such a ligand that is dimethyl-substituted in the 4-position of the oxazolines: S. Bellemin-Laponnaz, L. H. Gade, Chem. Commun. 2002, 1286; however, we found that for steric reasons, this substitution pattern normally precludes the coordination of this ligand as a tripod to a single metal center, and this also seems to be the case for the scandium complexes. Since the unsubstituted oxazoline derivatives were unstable und thus inaccessible, we are unable to perform this experiment.
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