Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 25, Issue 30, Pages 7298-7302Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201901269
Keywords
active species; catalyst degradation; diene polymerization; DOSY NMR spectroscopy; rare earth metals
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Funding
- German Science Foundation [AN 238/14-2]
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When activated with fluorinated borate cocatalysts the trimetallic complexes [Cp*LnMe(2)](3) (Ln=Y, Lu; Cp*=C5Me5) promote efficiently the formation of high-cis polybutadiene. Respective polyisoprenes instead bear much less pronounced microstructures, but reveal crosslinked products at lower polymerization temperatures. Varying the amount of cocatalyst, the emerging active species were examined by NMR spectroscopic techniques (incl. H-1 DOSY). The occurrence of donor-solvent and thermally induced degradation products of the highly reactive precatalyst [Cp*YMe2](3) and derived catalyst species was revealed by the elucidation of methylidene clusters [Cp*3Y3Me4(CH2)(thf)(2)] and [Cp*6Y6Me4(CH2)(4)], as well as [(Cp*Y)(2)Me-2(N(Me)(2)(C6H4)](n)[B(C6F5)(4)](n), implying a multimetallic active species.
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