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Title: Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework

Abstract

Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C 6 H 4 CH 2 ) 3 N] 3- (TriNO x 3- ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5-(CF 3 ) 2 -C 6 H 3 , and [Ce(TriNO x )py][OTf] . A rare complete Ce-halide series, Ce(TriNO x )X, in which X=F - , Cl - , Br - , I - , was also synthesized. We explored the solution chemistry of these complexes through detailed solution-phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X - group. DFT calculations on the series of calculations corroborated the experimental findings. Also, the use of a bulky and strongly donating tethered tripodal nitroxide ligand allowed the controlled redox chemistry at cerium. As a result, rare examples of cationic Ce IV complexes were synthesized and fully characterized. The full Ce-halidemore » series supported by the tripodal ligand framework is also reported (see scheme).« less

Authors:
 [1];  [1];  [1];  [2];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1378668
Grant/Contract Number:  
AC02-05CH11231; SC0006518
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 49; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cerium; density functional calculations; electrochemistry; nitroxides; redox chemistry

Citation Formats

Bogart, Justin A., Lippincott, Connor A., Carroll, Patrick J., Booth, Corwin H., and Schelter, Eric J. Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework. United States: N. p., 2015. Web. doi:10.1002/chem.201502952.
Bogart, Justin A., Lippincott, Connor A., Carroll, Patrick J., Booth, Corwin H., & Schelter, Eric J. Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework. United States. doi:10.1002/chem.201502952.
Bogart, Justin A., Lippincott, Connor A., Carroll, Patrick J., Booth, Corwin H., and Schelter, Eric J. Tue . "Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework". United States. doi:10.1002/chem.201502952. https://www.osti.gov/servlets/purl/1378668.
@article{osti_1378668,
title = {Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework},
author = {Bogart, Justin A. and Lippincott, Connor A. and Carroll, Patrick J. and Booth, Corwin H. and Schelter, Eric J.},
abstractNote = {Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C 6 H 4 CH 2 ) 3 N] 3- (TriNO x 3- ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5-(CF 3 ) 2 -C 6 H 3 , and [Ce(TriNO x )py][OTf] . A rare complete Ce-halide series, Ce(TriNO x )X, in which X=F - , Cl - , Br - , I - , was also synthesized. We explored the solution chemistry of these complexes through detailed solution-phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X - group. DFT calculations on the series of calculations corroborated the experimental findings. Also, the use of a bulky and strongly donating tethered tripodal nitroxide ligand allowed the controlled redox chemistry at cerium. As a result, rare examples of cationic Ce IV complexes were synthesized and fully characterized. The full Ce-halide series supported by the tripodal ligand framework is also reported (see scheme).},
doi = {10.1002/chem.201502952},
journal = {Chemistry - A European Journal},
number = 49,
volume = 21,
place = {United States},
year = {Tue Oct 27 00:00:00 EDT 2015},
month = {Tue Oct 27 00:00:00 EDT 2015}
}

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Cited by: 18 works
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Works referenced in this record:

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