Synthesis and characterisation of η6-arene (halogenidoaluminato)-lanthanoid(II) and alkaline earth(II) complexes
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.
| Item ID: | 74232 |
|---|---|
| Item Type: | Article (Research - C1) |
| ISSN: | 1873-3719 |
| Keywords: | Lanthanoids, Group 2, Aluminium, Arene complexes, Halides |
| Copyright Information: | © 2022 Elsevier Ltd. All rights reserved. Accepted Version: © 2022. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ |
| Funders: | Australian Research Council (ARC) |
| Projects and Grants: | ARC DP190100798 |
| Date Deposited: | 18 May 2022 08:19 |
| 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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