Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

Lu, Erli and Cooper, Oliver J. and McMaster, Jonathan and Tuna, Floriana and McInnes, Eric J.L. and Lewis, William and Blake, Alexander J. and Liddle, Stephen T. (2014) Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex. Angewandte Chemie International Edition, 53 (26). pp. 6696-6700. ISSN 1521-3773

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Abstract

We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] (5, BIPMTMS=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 trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPMTMS)(O)2(DMAP)2] (6).

Item Type: Article
Keywords: carbene ligands; imido ligands; multiple bonding; oxo ligands; uranium
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1002/anie.201403892
Depositing User: Lewis, William
Date Deposited: 28 Sep 2017 09:43
Last Modified: 14 Oct 2017 08:28
URI: http://eprints.nottingham.ac.uk/id/eprint/46639

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