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.

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