Divalent Lanthanide Tetraisobutylaluminates: Reactivity and Living Isoprene Polymerization

被引：0

作者：

Moinet, Eric C. ^{[1
]}

Wolf, Benjamin M. ^{[1
]}

Tardif, Olivier ^{[2
]}

Maichle-Moessmer, Caecilia ^{[1
]}

Anwander, Reiner ^{[1
]}

机构：

[1] Eberhard Karls Univ Tubingen, Inst Anorgan Chem, Morgenstelle 18, D-72076 Tubingen, Germany

[2] Bridgestone Corp, Ogawahigashi Cho, Kodaira, Tokyo 1878531, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 17期

关键词：

Cluster; Isobutylaluminate; Lanthanides; Living Isoprene Polymerization; Single-Component Catalyst; RARE-EARTH-METALS; STEREOSPECIFIC POLYMERIZATION; STRUCTURAL-CHARACTERIZATION; COMPLEXES BEARING; CATALYSTS; YTTRIUM; DIENES; YTTERBIUM(II); ACTIVATION; INSIGHTS;

D O I：

10.1002/anie.202219316

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Lanthanide (Ln) tetraisobutylaluminates constitute key components in commercial 1,3-diene polymerization catalysts, and likewise are the homogeneous rare-earth-metal catalysts of prime industrial importance. Discrete divalent rare-earth-metal complexes [Ln(AliBu(4))(2)] (Ln=Sm, Eu, Yb) reported here display the first structurally characterized homoleptic metal tetraisobutylaluminates. Treatment of [Ln(AliBu(4))(2)] with C2Cl6 gives access to Sm-II/Sm-III mixed-valence cluster [Sm6Cl8(AliBu(4))(6)] and the Yb-II cluster [Yb4Cl4(AliBu(4))(4)], respectively. Reaction with B(C6F5)(3) leads to hydride abstraction and formation of arene-coordinated hydroborates such as [Sm{HB(C6F5)(3)}(2)(toluene)(2)]. Complexes [Ln(AliBu(4))(2)] engage in single-component isoprene polymerization, affording high cis-1,4 polyisoprenes with narrow molecular weight distributions. Binary [Yb(AliBu(4))(2)]/[HNPhMe2][B(C6F5)(4)] fabricates polyisoprene in a perfectly living manner. The catalytically active species are scrutinized by NMR spectroscopy.

引用

页数：11

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