Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium

The homoleptic complexes of cerium with the tris­(piperidinyl)­imidophosphorane ligand, [NP­(pip)3]−, present the most negative Ce3+/4+ redox couple known (4.0 V shift from the Ce3+/4+ couple in 1 M HClO4(aq)] is established through reactivity studies. Spectroscopic studies (UV–vis, electron paramag...

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Bibliographic Details
Published in:Inorganic chemistry 2019-04, Vol.58 (8), p.5289-5304
Main Authors: Rice, Natalie T, Su, Jing, Gompa, Thaige P, Russo, Dominic R, Telser, Joshua, Palatinus, Lukas, Bacsa, John, Yang, Ping, Batista, Enrique R, La Pierre, Henry S
Format: Article
Language:English
Subjects:
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary:The homoleptic complexes of cerium with the tris­(piperidinyl)­imidophosphorane ligand, [NP­(pip)3]−, present the most negative Ce3+/4+ redox couple known (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.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.9b00368