Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes

Ali, Safaa H., Shephard, Angus C.G., Wang, Jun, Guo, Zhifang, Davies, Murray S., Deacon, Glen B., and Junk, Peter C. (2022) Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes. Chemistry: an Asian journal, 17 (5). e202101328.

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Abstract

Several new trivalent dinuclear rare earth 2,2’-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp²¯) complexes with the general form [Ln₂(mbmp)₃(thf)n] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp)₂(thf)₂] (5) have been synthesised by RTP (redox transmetallation/protolysis) reactions from lanthanoid metals, Hg(C₆F₅)₂ and the biphenol mbmpH₂. These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf)n] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n-butyllithium, both molecular ([Li(thf)₂Ln(mbmp)₂(thf)n] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf)₄][Ln(mbmp)₂(thf)₂] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe₂Ln(mbmp)₂(thf)₂] (Ln=Pr 15, Sm 16, and Tb 17)) and ionic [La(mbmp)(thf)₅][AlMe₂(mbmp)] (18) complexes. One gadolinium-potassium ([K(thf)₃Gd(mbmp)₂(thf)₂] (19)), and one ytterbium-zinc species ([ZnEtYb(mbmp)₂(thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively.

Item ID: 74606
Item Type: Article (Research - C1)
ISSN: 1861-471X
Keywords: biphenolate ligands, coordination chemistry, heterobimetallic complexes, rare earth complexes, redox transmetallation
Copyright Information: © 2022 The Authors. Chemistry - An Asian 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: DP190100798
Date Deposited: 23 Aug 2022 02:02
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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