Cerium(III/IV) Formamidinate Chemistry,and a Stable Cerium(IV) Diolate |
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| Authors: | Daniel Werner Prof?Dr Glen B Deacon Prof?Dr Peter C Junk Prof?Dr Reiner Anwander |
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| Affiliation: | 1. School of Chemistry, Monash University, Victoria 3800 (Australia);2. School of Pharmacy and Molecular Sciences, James Cook University, Townsville, Queensland 4811 (Australia);3. Institut für Anorganische Chemie, Auf der Morgenstelle 18, 72076 Tübingen (Germany) |
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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. |
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| Keywords: | cerium formamidinate oxidation protonolysis silylamide |
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