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Neodymium(III) Complexes Capable of Multi‐Electron Redox Chemistry
Author(s) -
Coughlin Ezra J.,
Zeller Matthias,
Bart Suzanne C.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201705423
Subject(s) - redox , neodymium , chemistry , electron , nanotechnology , inorganic chemistry , materials science , physics , laser , optics , nuclear physics
A family of neodymium complexes featuring a redox‐active ligand in three different oxidation states has been synthesized, including the iminoquinone (L 0 ) derivative, ( dipp iq) 2 NdI 3 ( 1‐iq ), the iminosemiquinone (L 1− ) compound, ( dipp isq) 2 NdI(THF) ( 1‐isq ), and the amidophenolate (L 2− ) [K(THF) 2 ][( dipp ap) 2 Nd(THF) 2 ] ( 1‐ap ) and [K(18‐crown‐6)][( dipp ap) 2 Nd(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)][( dipp isq) 2 Nd(S 5 )] ( 2‐isq crown ) and [K(18‐crown‐6)(THF)][( dipp isq) 2 Nd(Se 5 )] ( 3‐isq crown ), which are characterized to contain a 6‐membered twist‐boat ring.