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Updated: Oct 6, 2025

Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging
Published on: July 21, 2011
Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes
Safaa H Ali1, Angus C G Shephard1, Jun Wang1
1College of Science & Engineering, James Cook University, Townsville, QLD, 4811, Australia.
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(C6 F5 )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)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 ([AlMe2 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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