Hossain, Md. Elius, Guo, Zhifang, Wang, Jun, Deacon, Glen B., and Junk, Peter C. (2022) Synthesis and characterisation of η6-arene (halogenidoaluminato)-lanthanoid(II) and alkaline earth(II) complexes. Polyhedron, 217. 115737.

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Abstract

η6-Arene(iodidoaluminato)lanthanoid(II) complexes, {[Ln(η⁶-C₆H₅Me)(AlI₄)₂]}ₙ [Ln = Sm, 1, Eu, 2, Yb, 3; C₆H₅Me = toluene] have been prepared by reactions of in situ generated aluminium triiodide with the corresponding lanthanoid metals and 1,2-diiodoethane in toluene (molar ratio: 2:1:1). Compounds 1-3 are polymeric and the lanthanoid(II) atom of 1 and 2 is coordinated by an η⁶-arene and three chelating κ(I, I') tetraiodidoaluminate ligands, two of which are also bridging (LnI₂AlI₂Ln) and one is terminal. 3 is coordinated by an η⁶-arene, one terminal chelating κ(I, I') and one chelating and bridging (YbI₂AlI₂Yb) tetraiodidoaluminate ligand, and one monodentate tetraiodidoaluminate ligand, which is also bridging (YbIAl(I)I₂Yb). These are the first X-ray crystal structures of arene(tetrakisiodidoaluminato)lanthanoid(II) complexes. The first reported alkaline earth(II) (η⁶-arene)iodidoaluminate complexes, namely [Ca(η⁶-C₆H₅Me)(AlI₄)₂]ₙ (4), {[Sr(η⁶-C₆H₅Me)(AlI₄)₂]ₙ·nPhMe} (5), [Ba(η⁶-C₆H₅Me)₂(AlI₄)₂] (6), [Ca(η⁶-C₆H₃Me₃-1,3,5)(AlI₄)₂]ₙ (7) and {[Sr(η⁶-C₆H₃Me₃-1,3,5)AlI₄)₂]ₙ·0.5n(PhMe₃)} (8) have also been obtained in an arene (toluene or mesitylene) solution by a similar method. Complex 4 is isocoordinate with 3, and 5 is isomorphous with 2. Complex 7 has eight coordinate Ca similar to 4, and complex 8 has nine coordinate Sr as in 5. Mononuclear ten coordinate complex 6 is the first example of a monomeric eta(6)-arene sandwich complex of barium. The Eu-II bromidoaluminate complex {[Eu(η⁶-C₆H₅Me)(AlBr₄)₂]ₙ·0.5nPhMe} (9) has been prepared from Eu metal, AlBr3, and BrCH2CH2Br in toluene and has a unit cell similar to 8 despite the different metal and arene.

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