Synthesis, Electrochemistry, and Reactivity of Cerium(III/IV) Methylene-Bis-Phenolate Complexes
| Autor: | Patrick J. Carroll, Brian D. Mahoney, Eric J. Schelter, Nicholas A. Piro |
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| Rok vydání: | 2013 |
| Předmět: |
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Molecular Molecular Structure Phenol Ligand Inorganic chemistry chemistry.chemical_element Cerium Electrochemical Techniques Crystallography X-Ray Electrochemistry Medicinal chemistry Inorganic Chemistry Metal chemistry.chemical_compound chemistry Oxidation state visual_art Organometallic Compounds Benzophenone visual_art.visual_art_medium Reactivity (chemistry) Physical and Theoretical Chemistry Methylene |
| Zdroj: | Inorganic Chemistry. 52:5970-5977 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic400202r |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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