Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride
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) afforde...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Published: |
American Chemical Society
2014
|
| Online Access: | https://eprints.nottingham.ac.uk/35876/ |
| _version_ | 1848795180962938880 |
|---|---|
| author | King, David M. McMaster, Jonathan Tuna, Floriana McInnes, Eric J.L. Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_facet | King, David M. McMaster, Jonathan Tuna, Floriana McInnes, Eric J.L. Lewis, William Blake, Alexander J. Liddle, Stephen T. |
| author_sort | King, David M. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:28:00Z |
| format | Article |
| id | nottingham-35876 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:28:00Z |
| publishDate | 2014 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-358762020-05-04T16:47:09Z https://eprints.nottingham.ac.uk/35876/ 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. 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. American Chemical Society 2014-04-03 Article PeerReviewed King, David M., McMaster, Jonathan, Tuna, Floriana, McInnes, Eric J.L., Lewis, William, 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 http://pubs.acs.org/doi/abs/10.1021/ja502405e doi:10.1021/ja502405e doi:10.1021/ja502405e |
| spellingShingle | King, David M. McMaster, Jonathan Tuna, Floriana McInnes, Eric J.L. Lewis, William Blake, Alexander J. Liddle, Stephen T. Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride |
| title | Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride |
| title_full | Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride |
| title_fullStr | Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride |
| title_full_unstemmed | Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride |
| title_short | Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride |
| title_sort | synthesis and characterization of an f‑block terminal parent imido [u=nh] complex: a masked uranium(iv) nitride |
| url | https://eprints.nottingham.ac.uk/35876/ https://eprints.nottingham.ac.uk/35876/ https://eprints.nottingham.ac.uk/35876/ |