The preparation of new cerium(IV) complexes is highly desirable due to their potential applications in catalysis, redox chemistry, and materials synthesis. We have applied a rare earth/alkali metal/1,1'�BINOLate (REMB) heterobimetallic framework to synthesize a family of cerium(III) compounds, and probed the influence of secondary complex structure on electrochemical and chemical redox properties. Mild oxidation of the cerium(III) BINOLate compounds provides cerium(IV) complexes in excellent yield, and represent the first tetravalent derivatives of a REMB framework. The chemoselectivity observed for this system highlights the importance of inner sphere reorganization energy on oxidation reactions of cerium(III). The unique properties afforded by the tunable heterobimetallic framework will be discussed as a platform for the rational design of new cerium(IV) compounds.

Cerium BINOLate heterobimetallics: Impact of secondary complex structure on electrochemical and chemical redox properties

243rd National Meeting (2012)

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