Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride

King, David M. and McMaster, Jonathan and Tuna, Floriana and McInnes, Eric J.L. and Lewis, William and Blake, Alexander J. and Liddle, Stephen 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). pp. 5619-5622. ISSN 1520-5126

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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.

Item Type: Article
Schools/Departments: University of Nottingham UK Campus > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1021/ja502405e
Depositing User: Bramwell, Roseanna
Date Deposited: 17 Aug 2016 14:55
Last Modified: 19 Sep 2016 16:16
URI: http://eprints.nottingham.ac.uk/id/eprint/35876

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