Synthesis, Electrochemistry, and Reactivity of Cerium(III/IV) Methylene-Bis-Phenolate Complexes
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- 作者：Brian D. Mahoney ; Nicholas A. Piro ; Patrick J. Carroll ; Eric J. Schelter
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：May 20, 2013
- 年：2013
- 卷：52
- 期：10
- 页码：5970-5977
- 全文大小：401K
- 年卷期：v.52,no.10(May 20, 2013)
- ISSN：1520-510X
文摘
A series of cerium complexes containing a 2,2鈥?methylenebis(6-tert-butyl-4-methylphenolate) (MBP2鈥?/sup>) 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 鈭?.93 V vs Fc/Fc+. This potential demonstrates significant stabilization of the cerium(IV) ion in the MBP2鈥?/sup> framework with a shift of 2.25 V from the typically reported value for the cerium(III/IV) couple of E掳鈥?= +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鈥?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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