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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.

Journal Article Type Article
Publication Date Apr 16, 2014
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
APA6 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
DOI https://doi.org/10.1021/ja502405e
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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