Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry
Halim, Md Abdul, Guo, Zhifang, Deacon, Glen B., and Junk, Peter C. (2023) Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry. Chemistry - A European Journal, 29 (36). e202300956.
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Abstract
Divalent lanthanoid pseudo-Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N′-bis(2,6-di-isopropylphenyl)formamidine (DippFormH) to generate LnII complexes, namely [Ln(DippForm)Br(thf)3]2⋅6thf (1; Sm, 2; Eu), and [Yb(DippForm)Br(thf)2]2⋅2thf (3; Yb). Samarium and europium (in 1 and 2) are seven coordinate, whereas ytterbium (in 3) is six coordinate, and all are bromine-bridged dimers. When PhLnBr reacts with 3,5-diphenylpyrazole (Ph2pzH), both divalent (5; [Eu(Ph2pz)2(thf)4]) and trivalent (4 a; [Sm(Ph2pz)3(thf)3]⋅3thf, 4 b; [Sm(Ph2pz)3(dme)2]⋅dme) complexes are obtained. In the monomeric compounds 4(a,b), samarium is nine coordinate but europium is eight coordinate in 5. The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.
| Item ID: | 79047 |
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| Item Type: | Article (Research - C1) |
| ISSN: | 1521-3765 |
| Keywords: | bromine-bridge dimers, crystal structures, europium, lanthanoid(II) complexes, oxidative addition, Pseudo-Grignard reagents, samarium, ytterbium |
| Copyright Information: | © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
| Funders: | Australian Research Council (ARC) |
| Projects and Grants: | ARC DP230100112 |
| Date Deposited: | 19 Jul 2023 03:12 |
| 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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