Neodymium(III) Complexes Capable of Multi‐Electron Redox Chemistry

A family of neodymium complexes featuring a redox‐active ligand in three different oxidation states has been synthesized, including the iminoquinone (L0) derivative, (dippiq)2NdI3 (1‐iq), the iminosemiquinone (L1−) compound, (dippisq)2NdI(THF) (1‐isq), and the amidophenolate (L2−) [K(THF)2][(dippap)...

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Bibliographic Details
Published in:Angewandte Chemie 2017-09, Vol.129 (40), p.12310-12313
Main Authors: Coughlin, Ezra J., Zeller, Matthias, Bart, Suzanne C.
Format: Article
Language:English
Subjects:
Aquatic plants
Chemistry
Coordination compounds
Dipping
Lanthanoide
Ligands
Neodym
Neodymium
Oxidation
Oxidationen
Redoxaktive Liganden
Reduktionen
Structural analysis
Valence
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Summary:A family of neodymium complexes featuring a redox‐active ligand in three different oxidation states has been synthesized, including the iminoquinone (L0) derivative, (dippiq)2NdI3 (1‐iq), the iminosemiquinone (L1−) compound, (dippisq)2NdI(THF) (1‐isq), and the amidophenolate (L2−) [K(THF)2][(dippap)2Nd(THF)2] (1‐ap) and [K(18‐crown‐6)][(dippap)2Nd(THF)2] (1‐ap crown) species. Full spectroscopic and structural characterization of each derivative established the +3 neodymium oxidation state with redox chemistry occurring at the ligand rather than the neodymium center. Oxidation with elemental chalcogens showed the reversible nature of the ligand‐mediated reduction process, forming the iminosemiquinone metallocycles, [K(18‐crown‐6)][(dippisq)2Nd(S5)] (2‐isq crown) and [K(18‐crown‐6)(THF)][(dippisq)2Nd(Se5)] (3‐isq crown), which are characterized to contain a 6‐membered twist‐boat ring. Eine neue Wendung in der Ln3+‐Chemie: Eine Familie von Neodymkomplexen mit einem redoxaktiven Liganden in drei unterschiedlichen Oxidationszuständen wurde synthetisiert. Experimentelle Studien belegen das Vorliegen von NdIII‐Zentren und zeigen Redoxprozesse am Liganden auf. Die reversible Natur des ligandvermittelten Reduktionsprozesses wird durch Oxidationen mit elementaren Chalkogenen nachgewiesen.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201705423