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

Author:
Damon, Peter L., Wu, Guang, Kaltsoyannis, Nikolas, Hayton, Trevor W.
Source:
Journal of the American Chemical Society 2016 v.138 no.39 pp. 12743-12746
ISSN:
1520-5126
Subject:
ligands, nitrate reduction, nitrates, quantum mechanics
Abstract:
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.
Agid:
5560547