Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

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Reaction of Ce(NO3)3(THF)4 with Li3(THF)3(NN’3) (NN’3 = N(CH2CH2NR)3, R = SitBuMe2) in Et2O, in the presence of 12-crown-4, results in the formation of [Li(12-crown-4)][(NN’3)Ce(O)] (1) in 36% yield. This transformation proceeds via formation of a Ce(III) nitrate intermediate, [Li(12-crown-4)][(NN’3)Ce(κ2-O2NO)] (2), which undergoes inner sphere nitrate reduction. In addition, reaction of 1 with tBuMe2SiCl results in the formation of (NN’3)Ce(OSitBuMe2) (3), confirming the nucleophilic character of its oxo ligand. Natural bond orbital and quantum theory of atoms in molecules data reveal the Ce–O interaction in 1 to be significantly covalent, and strikingly similar to analogous U–O bonding.

Bibliographical metadata

Original languageEnglish
Pages (from-to)12743–12746
JournalJournal of the American Chemical Society
Issue number39
StatePublished - 13 Sep 2016