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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.

Authors

Erli Lu

Oliver J. Cooper

Floriana Tuna

Eric J.L. McInnes

William Lewis

Alexander J. Blake

Stephen T. Liddle



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 http://eprints.nottingham.ac.uk/id/eprint/46639
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/anie.201403892/abstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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