[UIII{N(SiMe2tBu)2}3]: A Structurally Authenticated Trigonal Planar Actinide Complex. Issue 45 (21st September 2014)

• Record Type: Journal Article
• Authors: Goodwin, Conrad A. P.; Tuna, Floriana; McInnes, Eric J. L.; Liddle, Stephen T.; McMaster, Jonathan; Vitorica‐Yrezabal, Inigo J.; Mills, David P.
• Is Part Of: Chemistry. Volume 20:Issue 45(2014)
• Page Start: 14579
• Page End: 14583
• Publication Date: 2014-09-21
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201404864
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>We report the synthesis and characterization of the uranium(III) triamide complex [U^III(N**)₃] [<bold>1</bold>, N**=N(SiMe₂<italic>t</italic>Bu)₂⁻]. Surprisingly, complex <bold>1</bold> exhibits a trigonal planar geometry in the solid state, which is unprecedented for three‐coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [U^III(N**)₃] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [U^III(N")₃] (N"=N(SiMe₃)₂⁻), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [U^III(N")₃], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of <bold>1</bold> leads to favorable magnetic dynamics, which may be considered in the future design of U^III single‐molecule magnets.</p> </abstract>