Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction | Health & Environmental Research Online (HERO)

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Citation
Tags

HERO ID

3424953

Reference Type

Journal Article

Title

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

Author(s)

Damon, PL; Wu, G; Kaltsoyannis, N; Hayton, TW

Year

2016

Is Peer Reviewed?

Yes

Journal

Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126

Volume

138

Issue

Page Numbers

12743-12746

Language

English

PMID

27622564

DOI

10.1021/jacs.6b07932

Web of Science Id

WOS:000384952100009

Abstract

Reaction of Ce(NO3)3(THF)4 with Li3(THF)3(NN'3) (NN'3 = N(CH2CH2NR)3, R = Si(t)BuMe2) 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(κ(2)-O2NO)] (2), which undergoes inner sphere nitrate reduction. In addition, reaction of 1 with (t)BuMe2SiCl results in the formation of (NN'3)Ce(OSi(t)BuMe2) (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.