Dalton Transactions (Print Edition) 2014-11-21

Variation of electronic transitions and reduction potentials of cerium(IV) complexes.

Ursula J Williams, David Schneider, Walter L Dorfner, Cäcilia Maichle-Mössmer, Patrick J Carroll, Reiner Anwander, Eric J Schelter

Index: Dalton Trans. 43(43) , 16197-206, (2014)

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Abstract

The trivalent compound K[Ce[N(SiHMe2)2]4] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)2]4. Protonolysis reactions of Ce[N(SiHMe2)2]4 with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce(O(t)Bu)4(py)2, Ce2(OCH2C6R5)8(thf)2 (R = Me, F), and Ce(Odpp)4 (dpp = 2,6-(C6H5)2-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.