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

Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C.

doi:10.1002/anie.201705423

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

Journal Article · Tue Aug 01 00:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201705423· OSTI ID:1533115

Coughlin, Ezra J. ^[1]; Zeller, Matthias ^[1];

^[1]

Purdue Univ., West Lafayette, IN (United States)

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.

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Research Organization:: Purdue Univ., West Lafayette, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0008479; CHE 1625543

OSTI ID:: 1533115

Alternate ID(s):: OSTI ID: 1377946

Journal Information:: Angewandte Chemie (International Edition), Vol. 56, Issue 40; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Steric Influence and Intermolecular Interactions of Formamidinate Ligands in Lanthanide (Sm, Yb) Arylchalcogenolate Complexes: Steric Influence and Intermolecular Interactions of Formamidinate Ligands in Lanthanide (Sm, Yb) Arylchalcogenolate Complexes Ma, Ying-Zhao; Pushkarevsky, Nikolay A.; Sukhikh, Taisiya S. European Journal of Inorganic Chemistry, Vol. 2018, Issue 29 https://doi.org/10.1002/ejic.201800201	journal	August 2018
Europium and ytterbium complexes with o -iminoquinonato ligands: synthesis, structure, and magnetic behavior Klementyeva, Svetlana V.; Lukoyanov, Anton N.; Afonin, Mikhail Yu. Dalton Transactions, Vol. 48, Issue 10 https://doi.org/10.1039/c8dt04849e	journal	January 2019
Study of the Possibility of Using Salt Metathesis Reactions for the Synthesis of the Neodymium and Samarium β-Diketiminate Chalcogenide Complexes. Unexpected Reduction of Sm(III) to Sm(II) Mironova, O. A.; Sukhikh, T. S.; Konchenko, S. N. Russian Journal of Coordination Chemistry, Vol. 46, Issue 4 https://doi.org/10.1134/s1070328420030057	journal	April 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 1551967: Experimental Crystal Structure Determination Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1p2yg5 The current record is supplemented by this dataset	dataset	January 2017
CCDC 1551968: Experimental Crystal Structure Determination Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1p2yh6 The current record is supplemented by this dataset	dataset	January 2017
CCDC 1551969: Experimental Crystal Structure Determination Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1p2yj7 The current record is supplemented by this dataset	dataset	January 2017
CCDC 1551970: Experimental Crystal Structure Determination Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1p2yk8 The current record is supplemented by this dataset	dataset	January 2017
CCDC 1551971: Experimental Crystal Structure Determination Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1p2yl9 The current record is supplemented by this dataset	dataset	January 2017
CCDC 1551972: Experimental Crystal Structure Determination Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. https://doi.org/10.5517/ccdc.csd.cc1p2ymb The current record is supplemented by this dataset	dataset	January 2017