η6-Arene(halogenidoaluminato)lanthanoid(III) Complexes: Synthesis, Characterization and Catalytic Activity for Isoprene Polymerization

Hossain, Md Elius, Guo, Zhifang, Wang, Jun, Deacon, Glen B., Junk, Peter C., Diether, Dominic, and Anwander, Reiner (2022) η6-Arene(halogenidoaluminato)lanthanoid(III) Complexes: Synthesis, Characterization and Catalytic Activity for Isoprene Polymerization. European Journal of Inorganic Chemistry, 2022 (7). e202101009.

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Abstract

η6-Arene(iodido-/bromido-aluminato)lanthanoid(III) complexes, [Ln(η⁶-C₆H₅Me)(AlI₄)₃] [Ln=La (1), Ce (2), Nd (3), (Gd) (4); C₆H₅Me=toluene], [Ln(η⁶-C₆H₃Me₃-1,3,5)(AlI₄)₃] [Ln=La (5), Ce (6), Pr (7), Nd (8), Sm (9), Gd (10); C₆H₃Me₃-1,3,5=mesitylene], and [Ln(η⁶-C₆H₅Me)(AlBr₄)₃] [Ln=La (11), Nd (12), Sm (13)] were prepared by reactions of aluminium triiodide or aluminium tribromide with the corresponding lanthanoid metals and 1,2-diiodoethane or 1,2-dibromoethane in an arene (toluene or mesitylene) solution (molar ratio : 6 : 2 : 3). The first X-ray crystal structures of arene(iodidoaluminato)lanthanoid(III) complexes are reported. The lanthanoid atom is coordinated by an η⁶-arene and three chelating κ(I, I')-tetraiodidoaluminato ligands. The tetrabromidoaluminate complexes have similar structures. The precatalyst 3 was treated with AlR₃ (R=Me or iBu) to give [Nd(η⁶-C₆H₅Me)(AlI₃R)₃] species in situ, which were then tested for catalytic activity towards isoprene polymerization. Although the resulting polyisoprene had a desirable high cis-1,4 content, the catalyst performance was well below known best performing systems and indicates that iodidoaluminates are the least favorable of the halogenidoaluminatolanthanoid(III) complexes.

Item ID: 73052
Item Type: Article (Research - C1)
ISSN: 1099-0682
Keywords: Aluminium, Arene ligands, Bromine, Iodine, Lanthanoids
Copyright Information: © 2022 Wiley-VCH GmbH. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Funders: Australian Research Council (ARC)
Projects and Grants: ARC DP190100798
Date Deposited: 16 Mar 2022 08:21
FoR Codes: 34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340203 F-block chemistry @ 100%
SEO Codes: 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280105 Expanding knowledge in the chemical sciences @ 100%
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