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  • Review Article
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Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls

Nature Chemistry volume 2, pages 257–268 (2010)Cite this article

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Abstract

This Review gives an overview on recent progress in the synthesis and chemistry of rare-earth metal dialkyl complexes bearing monoanionic ancillary ligands, with an emphasis on novel polymerization catalysts. These structurally well-defined and highly reactive compounds are prepared either by alkane elimination reactions between trialkyl rare-earth complexes and acidic neutral ligands, or by the metathetical reactions of rare-earth trihalides with the alkali metal salts of the corresponding ligands. On treatment with an appropriate borate compound, the dialkyl complexes are converted into the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a series of new polymer materials that exhibit novel properties. Alternatively, hydrogenation of the dialkyl rare-earth complexes with H2 affords a new class of rare-earth polyhydride complexes with unique features in terms of both their structure and reactivity.

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Figure 1: A general scheme showing the synthesis and important transformations of rare-earth dialkyls.
Figure 2: Synthesis of half-sandwich rare-earth dialkyl complexes.
Figure 3: Representative examples of rare-earth metal dialkyl complexes bearing monoanionic, non-Cp ligands.
Figure 4: Synthesis of cationic rare-earth alkyl complexes from dialkyl precursors.
Figure 5: Regio- and stereospecific polymerization of styrene and isoprene catalysed by cationic rare-earth alkyl complexes.
Figure 6: Half-sandwich Sc-catalysed copolymerization of various olefins.
Figure 7: Synthesis and reactions of polynuclear rare-earth polyhydride complexes bearing the C5Me4SiMe3 (Cp') ligand.
Figure 8: Synthesis of polynuclear rare-earth polyhydride complexes bearing mono-anionic, non-Cp ligands.

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Authors and Affiliations

  1. Organometallic Chemistry Laboratory, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198 Japan.,

    Masayoshi Nishiura & Zhaomin Hou

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  1. Masayoshi Nishiura
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  2. Zhaomin Hou
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Correspondence to Zhaomin Hou.

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Nishiura, M., Hou, Z. Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls. Nature Chem 2, 257–268 (2010). https://doi.org/10.1038/nchem.595

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