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.

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)(?-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 ?2?4 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: https://nottingham-repository.worktribe.com/output/727643
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/ja502405e