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Title: Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium

Abstract

We present that the homoleptic complexes of cerium with the tris(piperidinyl)imidophosphorane ligand, [NP(pip)3]-, present the most negative Ce3+/4+ redox couple known (<-2.64 V vs Fc/Fc+). This dramatic stabilization of the cerium tetravalent oxidation state [>4.0 V shift from the Ce3+/4+ couple in 1 M HClO4(aq)] is established through reactivity studies. Spectroscopic studies (UV–vis, electron paramagnetic resonance, and Ce L3-edge X-ray absorption spectroscopy), in conjunction with density functional theory studies, reveal the dominant covalent metal–ligand interactions underlying the observed redox chemistry and the dependence of the redox potential on the binding of potassium in the inner coordination sphere.

Authors:
 [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [3];  [4];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Roosevelt Univ., Chicago, IL (United States)
  4. Czech Academy of Sciences, Prague (Czechia)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1544689
Report Number(s):
LA-UR-18-31666
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
89233218CNA000001; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 8; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rice, Natalie T., Su, Jing, Gompa, Thaige P., Russo, Dominic R., Telser, Joshua, Palatinus, Lukas, Bacsa, John, Yang, Ping, Batista, Enrique Ricardo, and La Pierre, Henry S. Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b00368.
Rice, Natalie T., Su, Jing, Gompa, Thaige P., Russo, Dominic R., Telser, Joshua, Palatinus, Lukas, Bacsa, John, Yang, Ping, Batista, Enrique Ricardo, & La Pierre, Henry S. Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium. United States. doi:10.1021/acs.inorgchem.9b00368.
Rice, Natalie T., Su, Jing, Gompa, Thaige P., Russo, Dominic R., Telser, Joshua, Palatinus, Lukas, Bacsa, John, Yang, Ping, Batista, Enrique Ricardo, and La Pierre, Henry S. Wed . "Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium". United States. doi:10.1021/acs.inorgchem.9b00368. https://www.osti.gov/servlets/purl/1544689.
@article{osti_1544689,
title = {Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium},
author = {Rice, Natalie T. and Su, Jing and Gompa, Thaige P. and Russo, Dominic R. and Telser, Joshua and Palatinus, Lukas and Bacsa, John and Yang, Ping and Batista, Enrique Ricardo and La Pierre, Henry S.},
abstractNote = {We present that the homoleptic complexes of cerium with the tris(piperidinyl)imidophosphorane ligand, [NP(pip)3]-, present the most negative Ce3+/4+ redox couple known (<-2.64 V vs Fc/Fc+). This dramatic stabilization of the cerium tetravalent oxidation state [>4.0 V shift from the Ce3+/4+ couple in 1 M HClO4(aq)] is established through reactivity studies. Spectroscopic studies (UV–vis, electron paramagnetic resonance, and Ce L3-edge X-ray absorption spectroscopy), in conjunction with density functional theory studies, reveal the dominant covalent metal–ligand interactions underlying the observed redox chemistry and the dependence of the redox potential on the binding of potassium in the inner coordination sphere.},
doi = {10.1021/acs.inorgchem.9b00368},
journal = {Inorganic Chemistry},
number = 8,
volume = 58,
place = {United States},
year = {2019},
month = {4}
}

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