title: Variation of electronic transitions and reduction potentials of cerium(IV) complexes.
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.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA. schelter@sas.upenn.edu.
authors.forename: Ursula J
authors.initials: UJ
authors.lastname: Williams
authors.forename: David
authors.initials: D
authors.lastname: Schneider
authors.forename: Walter L
authors.initials: WL
authors.lastname: Dorfner
authors.forename: Cäcilia
authors.initials: C
authors.lastname: Maichle-Mössmer
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.forename: Reiner
authors.initials: R
authors.lastname: Anwander
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter