Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex

Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

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).

Citation

Lu, E., Cooper, O. J., McMaster, J., Tuna, F., McInnes, E. J., Lewis, W., …Liddle, S. T. (2014). Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex. Angewandte Chemie International Edition, 53(26), 6696-6700. https://doi.org/10.1002/anie.201403892

• Journal Article Type: Article
• Acceptance Date: Apr 1, 2014
• Online Publication Date: May 19, 2014
• Publication Date: Jun 23, 2014
• Deposit Date: Sep 28, 2017
• Publicly Available Date: Sep 28, 2017
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 53
• Issue: 26
• Pages: 6696-6700
• DOI: https://doi.org/10.1002/anie.201403892
• Keywords: carbene ligands; imido ligands; multiple bonding; oxo ligands; uranium
• Public URL: https://nottingham-repository.worktribe.com/output/730199
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/anie.201403892/abstract