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Updated: May 11, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Synthesis, electrochemistry, and reactivity of cerium(III/IV) methylene-bis-phenolate complexes
Brian D Mahoney1, Nicholas A Piro, Patrick J Carroll
1P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Abstract:
A series of cerium complexes containing a 2,2'-methylenebis(6-tert-butyl-4-methylphenolate) (MBP(2-)) ligand framework is described. Electrochemical studies of the compound [Li(THF)2Ce(MBP)2(THF)2] (1) reveal that the metal based oxidation wave occurs at -0.93 V vs Fc/Fc(+). This potential demonstrates significant stabilization of the cerium(IV) ion in the MBP(2-) framework with a shift of ∼2.25 V from the typically reported value for the cerium(III/IV) couple of E°' = +1.30 V vs Fc/Fc(+) for Ce(ClO4)3 in HClO4 solutions. Compound 1 undergoes oxidation to form stable cerium(IV) species in the presence of a variety of common oxidants. The coordination of the redox-active ligands 2,2'-bipyridine and benzophenone to 1 result in complexes in which no apparent metal-to-ligand charge transfer occurs and the cerium ion remains in the +3 oxidation state.
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