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

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((OBu)-Bu-t)(4)(py)(2), Ce-2(OCH2C6P5)(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.