Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex1. (19th May 2014)

• Record Type: Journal Article
• Authors: Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Tuna, Floriana; McInnes, Eric J. L.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.
• Is Part Of: Angewandte Chemie. Volume 126:Number 26(2014)
• Page Start: 6814
• Page End: 6818
• Publication Date: 2014-05-19
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201403892
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>We report the uranium(VI) carbene imido oxo complex [U(BIPM^TMS)(NMes)(O)(DMAP)₂] (<bold>5</bold>, BIPM^TMS=C(PPh₂NSiMe₃)₂; Mes=2, 4, 6‐Me₃C₆H₂; DMAP=4‐(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two‐electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T‐shaped motif with respect to the carbene, which is consistent with an inverse <italic>trans</italic>‐influence. Complex <bold>5</bold> reacts with <italic>tert</italic>‐butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM^TMS)(O)₂(DMAP)₂] (<bold>6</bold>).</p> </abstract>