Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

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• 作者：Jerome R. Robinson ; Zachary Gordon ; Corwin H. Booth ; Patrick J. Carroll ; Patrick J. Walsh ; Eric J. Schelter
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：December 18, 2013
• 年：2013
• 卷：135
• 期：50
• 页码：19016-19024
• 全文大小：503K
• 年卷期：v.135,no.50(December 18, 2013)
• ISSN：1520-5126

文摘

Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1鈥测€揃INOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.