1,3-Diene Polymerization Promoted by Half-Sandwich Rare-Earth-Metal Dimethyl Complexes: Active Species Clustering and Cationization/Deactivation Processes

被引：18
|
作者：
Hollfelder, Christoph O. [1 ]
Jende, Lars N. [1 ]
Dietrich, Hans-Martin [1 ]
Eichele, Klaus [1 ]
Maichle-Moessmer, Caecilia [1 ]
Anwander, Reiner [1 ]
机构：
[1] Eberhard Karls Univ Tubingen, Inst Anorgan Chem, Morgenstelle 18, D-72076 Tubingen, Germany
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 30期
关键词：
active species; catalyst degradation; diene polymerization; DOSY NMR spectroscopy; rare earth metals; STUDYING TRANSLATIONAL DIFFUSION; CATALYZED OLEFIN POLYMERIZATION; NUCLEAR-MAGNETIC-RESONANCE; H BOND ACTIVATION; STRUCTURAL-CHARACTERIZATION; ISOPRENE POLYMERIZATION; METHYLIDENE COMPLEXES; CHEMISTRY; REACTIVITY; LIGANDS;
D O I：
10.1002/chem.201901269
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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.
引用
收藏
页码：7298 / 7302
页数：5
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