Cerium(III/IV) formamidinate chemistry, and a stable cerium(IV) diolate

Werner, Daniel, Deacon, Glen B., Junk, Peter C., and Anwander, Reiner (2014) Cerium(III/IV) formamidinate chemistry, and a stable cerium(IV) diolate. Chemistry: a European journal, 20 (15). pp. 4426-4438.

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Abstract

Four new cerium(III) formamidinate complexes comprising [Ce(p-TolForm)(3)], [Ce(DFForm)(3)(thf)(2)], [Ce(DFForm)(3)], and [Ce(EtForm)(3)] were synthesized by protonolysis reactions using [Ce{N(SiMe3)(2)}(3)] and formamidines of varying functionality, namely N,N-bis(4-methylphenyl)formamidine (p-TolFormH), N,N-bis(2,6-difluorophenyl)formamidine (DFFormH), and the sterically more demanding N,N-bis(2,6-diethylphenyl)formamidine (EtFormH). The bimetallic cerium lithium complex [LiCe(DFForm)(4)] was synthesized by treating a mixture of [Ce{N(SiHMe2)(2)}(3)(thf)(2)] and [Li{N(SiHMe2)(2)}] with four equivalents of DFFormH in toluene. Oxidation of the trivalent cerium(III) formamidinate complexes by trityl chloride (Ph3CCl) caused dramatic color changes, although the cerium(IV) species appeared transient and reformed cerium(III) complexes and N-trityl-N,N-diarylformamidines shortly after oxidation. The first structurally characterized homoleptic cerium(IV) formamidinate complex [Ce(p-TolForm)(4)] was obtained through a protonolysis reaction between [Ce{N(SiHMe2)(2)}(4)] and four equivalents of p-TolFormH. [Ce{N(SiHMe2)(2)}(4)] was also treated with DFFormH and EtFormH, but the resulting cerium(IV) complexes decomposed before isolation was possible. The new cerium(IV) silylamide complex [Ce{N(SiMe3)(2)}(3)(bda)(0.5)](2) (bda=1,4-benzenediolato) was synthesized by treatment of [Ce{N(SiMe3)(2)}(3)] with half an equivalent of 1,4-benzoquinone, and showed remarkable resistance towards protonolysis or reduction.

Item ID: 33747
Item Type: Article (Refereed Research - C1)
Keywords: cerium, formamidinate, oxidation, protonolysis, silylamide
ISSN: 1521-3765
Funders: German Science Foundation (GSF), Australian Research Council (ARC)
Projects and Grants: GSF Grant AN 238/16-1, ARC Discovery: DP130100152
Date Deposited: 18 Jun 2014 09:51
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030202 f-Block Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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