Thermally Stable Uranium Dinitrogen Complex with Siloxide Supporting Ligands

Stephen M. Mansell, Joy H. Farnaby, Anne I. Germeroth, Polly L. Arnold*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

A new dinitrogen adduct of a homoleptic uranium tris(siloxide) complex, [U{OSi(Mes)(3)}(3)](2)(mu-eta(2):eta(2)-N-2), is reported. Synthesis of the N-15-labeled isotopomer and Raman spectroscopy confirm the reductive activation of N-2 to a (N-2)(2-) dianion. The N-15 NMR shift of the N-15(2)-labeled isotopomer is also reported. Crystallographic characterization shows a side-on (N-2)(2-) coordinated in either an eclipsed or staggered conformation in different crystals. The U-N-2-U complex is stable to vacuum and shows high thermal stability, retaining the formally reduced dinitrogen at 100 degrees C. The parent three-coordinate uranium(III) [U{OSi(Mes)(3)}(3)] could not be isolated in our hands, with N-2-free syntheses affording only uranium(IV) compounds. The rational synthesis and full characterization of two such U(IV) byproducts, [U{OSi(Mes)(3)}{N(SiMe3)(2)}(3)] and [U{OSi(Mes)(3)}(4)], is also reported.

Original languageEnglish
Pages (from-to)4214-4222
Number of pages9
JournalOrganometallics
Volume32
Issue number15
DOIs
Publication statusPublished - 12 Aug 2013

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