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Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride

King, David M.; McMaster, Jonathan; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

Authors

David M. King

Floriana Tuna

Eric J.L. McInnes

William Lewis

Alexander J. Blake

Stephen T. Liddle



Abstract

Deprotonation of [U(TrenTIPS)(NH2)] (1) [TrenTIPS = N(CH2CH2NSiPri3)3] with organoalkali metal reagents MR (M = Li, R = But; M = Na−Cs, R = CH2C6H5) afforded the imido-bridged dimers [{U-(TrenTIPS)(μ-N[H]M)}2] [M = L −Cs (2a−e)]. Treatmentof 2c (M = K) with 2 equiv of 15 crown-5 ether (15C5) afforded the uranium terminal parent imido complex [U(TrenTIPS)(NH)][K(15C5)2] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium−imido linkage was found to be essentially linear, and theoretical calculations suggested σ2π4 polarized U−N multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(TrenTIPS)(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium−nitride complex [U(TrenTIPS)(N)] (5); this reaction is a new way to prepare the terminal uranium−nitride linkage and was calculated to be exothermic by −3.25 kcal mol−1.

Citation

King, D. M., McMaster, J., Tuna, F., McInnes, E. J., Lewis, W., Blake, A. J., & Liddle, S. T. (2014). Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride. Journal of the American Chemical Society, 136(15), 5619-5622. https://doi.org/10.1021/ja502405e

Journal Article Type Article
Acceptance Date Mar 12, 2014
Online Publication Date Apr 8, 2014
Publication Date Apr 16, 2014
Deposit Date Aug 17, 2016
Publicly Available Date Aug 17, 2016
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 136
Issue 15
Pages 5619-5622
DOI https://doi.org/10.1021/ja502405e
Public URL http://eprints.nottingham.ac.uk/id/eprint/35876
Publisher URL http://pubs.acs.org/doi/abs/10.1021/ja502405e
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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