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

Journal Article · · Angewandte Chemie
 [1];  [1]; ORCiD logo [1]
  1. H.C. Brown Laboratory Department of Chemistry Purdue University West Lafayette IN 47907 USA
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Abstract 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.

Sponsoring Organization:
USDOE
OSTI ID:
1377947
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 129 Journal Issue: 40; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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