Divalent Lanthanide Tetraisobutylaluminates: Reactivity and Living Isoprene Polymerization |
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| Authors: | Eric C Moinet Dr Benjamin M Wolf Dr Olivier Tardif Dr Cäcilia Maichle-Mössmer Prof?Dr Reiner Anwander |
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| Institution: | 1. Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany;2. Bridgestone Corporation Ogawahigashi-cho, Kodaira-shi, Tokyo, 187-8531 Japan |
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| Abstract: | 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(AliBu4)2] (Ln=Sm, Eu, Yb) reported here display the first structurally characterized homoleptic metal tetraisobutylaluminates. Treatment of Ln(AliBu4)2] with C2Cl6 gives access to SmII/SmIII mixed-valence cluster Sm6Cl8(AliBu4)6] and the YbII cluster Yb4Cl4(AliBu4)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(AliBu4)2] engage in single-component isoprene polymerization, affording high cis-1,4 polyisoprenes with narrow molecular weight distributions. Binary Yb(AliBu4)2]/HNPhMe2]B(C6F5)4] fabricates polyisoprene in a perfectly living manner. The catalytically active species are scrutinized by NMR spectroscopy. |
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| Keywords: | Cluster Isobutylaluminate Lanthanides Living Isoprene Polymerization Single-Component Catalyst |
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