Synthesis, Electrochemistry, and Reactivity of Cerium(III/IV) Methylene-Bis-Phenolate Complexes

A series of cerium complexes containing a 2,2′-methylenebis(6-tert-butyl-4-methylphenolate) (MBP2–) 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...

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Bibliographic Details
Published in:Inorganic chemistry 2013-05, Vol.52 (10), p.5970-5977
Main Authors: Mahoney, Brian D, Piro, Nicholas A, Carroll, Patrick J, Schelter, Eric J
Format: Article
Language:English
Subjects:
Cerium - chemistry
Crystallography, X-Ray
Electrochemical Techniques
Models, Molecular
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Phenol - chemistry
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Summary:A series of cerium complexes containing a 2,2′-methylenebis(6-tert-butyl-4-methylphenolate) (MBP2–) 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 MBP2– 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.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic400202r