期刊
CHEMISTRY-AN ASIAN JOURNAL
卷 17, 期 5, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.202101328
关键词
biphenolate ligands; coordination chemistry; heterobimetallic complexes; rare earth complexes; redox transmetallation
资金
- Australian Research Council [DP190100798]
Several new trivalent dinuclear rare earth complexes were synthesized using RTP reactions. These complexes react with lithium, aluminium, potassium, and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species.
Several new trivalent dinuclear rare earth 2,2'-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp(2-)) complexes with the general form [Ln(2)(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 mbmpH(2). 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)(2)Ln(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 ([AlMe(2)Ln(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)(3)Gd(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.
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