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Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium

Journal Article · · Inorganic Chemistry
 [1];  [2];  [1];  [1];  [3];  [4];  [1];  [2];  [2];  [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)
+ Show Author Affiliations
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.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
89233218CNA000001; AC02-76SF00515
OSTI ID:
1544689
Report Number(s):
LA-UR--18-31666
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 8 Vol. 58; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (5)

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