Open AccessHomoleptic Imidophosphorane Stabilization of Tetravalent Cerium
Author(s) -
Natalie T. Rice,
Jing Su,
Thaige P. Gompa,
Dominic R. Russo,
Joshua Telser,
Lukáš Palatinus,
John Bacsa,
Ping Yang,
Enrique R. Batista,
Henry S. La Pierre
Publication year - 2019
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.9b00368
Subject(s) - chemistry , homoleptic , cerium , redox , coordination sphere , ligand (biochemistry) , oxidation state , reactivity (psychology) , inorganic chemistry , metal , electron paramagnetic resonance , covalent bond , density functional theory , crystallography , photochemistry , computational chemistry , nuclear magnetic resonance , organic chemistry , medicine , biochemistry , physics , receptor , alternative medicine , pathology
The homoleptic complexes of cerium with the tris(piperidinyl)imidophosphorane ligand, [NP(pip) 3 ] - , present the most negative Ce 3+/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 Ce 3+/4+ couple in 1 M HClO 4 (aq)] is established through reactivity studies. Spectroscopic studies (UV-vis, electron paramagnetic resonance, and Ce L 3 -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.
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