Neodymium(III) Complexes Capable of Multi-Electron Redox Chemistry
Abstract
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.
- Publication Date:
- Research Org.:
- Purdue Univ., West Lafayette, IN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1533115
- Alternate Identifier(s):
- OSTI ID: 1377946
- Grant/Contract Number:
- SC0008479; CHE 1625543
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 40; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; lanthanide; neodymium; oxidation; redox-active ligand; reduction
Citation Formats
Coughlin, Ezra J., Zeller, Matthias, and Bart, Suzanne C. Neodymium(III) Complexes Capable of Multi-Electron Redox Chemistry. United States: N. p., 2017.
Web. doi:10.1002/anie.201705423.
Coughlin, Ezra J., Zeller, Matthias, & Bart, Suzanne C. Neodymium(III) Complexes Capable of Multi-Electron Redox Chemistry. United States. https://doi.org/10.1002/anie.201705423
Coughlin, Ezra J., Zeller, Matthias, and Bart, Suzanne C. Tue .
"Neodymium(III) Complexes Capable of Multi-Electron Redox Chemistry". United States. https://doi.org/10.1002/anie.201705423. https://www.osti.gov/servlets/purl/1533115.
@article{osti_1533115,
title = {Neodymium(III) Complexes Capable of Multi-Electron Redox Chemistry},
author = {Coughlin, Ezra J. and Zeller, Matthias and Bart, Suzanne C.},
abstractNote = {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.},
doi = {10.1002/anie.201705423},
journal = {Angewandte Chemie (International Edition)},
number = 40,
volume = 56,
place = {United States},
year = {Tue Aug 01 00:00:00 EDT 2017},
month = {Tue Aug 01 00:00:00 EDT 2017}
}
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