UC Santa Barbara

Reaction of Ce(NO₃)₃(THF)₄ with Li₃(THF)₃(NN'₃) (NN'₃ = N(CH₂CH₂NR)₃, R = Si^tBuMe₂) 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(OSi^tBuMe₂) (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.