Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] (5, BIPMTMS=C(PPh2NSiMe3)2; Mes=2,4,6-Me3C6H2; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms d...

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Main Authors: Lu, Erli, Cooper, Oliver J., McMaster, Jonathan, Tuna, Floriana, McInnes, Eric J.L., Lewis, William, Blake, Alexander J., Liddle, Stephen T.
Format: Article
Published: Wiley-VCH Verlag 2014
Subjects:
Online Access:https://eprints.nottingham.ac.uk/46639/
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author Lu, Erli
Cooper, Oliver J.
McMaster, Jonathan
Tuna, Floriana
McInnes, Eric J.L.
Lewis, William
Blake, Alexander J.
Liddle, Stephen T.
author_facet Lu, Erli
Cooper, Oliver J.
McMaster, Jonathan
Tuna, Floriana
McInnes, Eric J.L.
Lewis, William
Blake, Alexander J.
Liddle, Stephen T.
author_sort Lu, Erli
building Nottingham Research Data Repository
collection Online Access
description We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] (5, BIPMTMS=C(PPh2NSiMe3)2; Mes=2,4,6-Me3C6H2; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPMTMS)(O)2(DMAP)2] (6).
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spelling nottingham-466392020-05-04T16:49:08Z https://eprints.nottingham.ac.uk/46639/ Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex Lu, Erli Cooper, Oliver J. McMaster, Jonathan Tuna, Floriana McInnes, Eric J.L. Lewis, William Blake, Alexander J. Liddle, Stephen T. We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] (5, BIPMTMS=C(PPh2NSiMe3)2; Mes=2,4,6-Me3C6H2; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPMTMS)(O)2(DMAP)2] (6). Wiley-VCH Verlag 2014-06-23 Article PeerReviewed Lu, Erli, Cooper, Oliver J., McMaster, Jonathan, Tuna, Floriana, McInnes, Eric J.L., Lewis, William, Blake, Alexander J. and Liddle, Stephen T. (2014) Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex. Angewandte Chemie International Edition, 53 (26). pp. 6696-6700. ISSN 1521-3773 carbene ligands; imido ligands; multiple bonding; oxo ligands; uranium http://onlinelibrary.wiley.com/doi/10.1002/anie.201403892/abstract doi:10.1002/anie.201403892 doi:10.1002/anie.201403892
spellingShingle carbene ligands; imido ligands; multiple bonding; oxo ligands; uranium
Lu, Erli
Cooper, Oliver J.
McMaster, Jonathan
Tuna, Floriana
McInnes, Eric J.L.
Lewis, William
Blake, Alexander J.
Liddle, Stephen T.
Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex
title Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex
title_full Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex
title_fullStr Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex
title_full_unstemmed Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex
title_short Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex
title_sort synthesis, characterization, and reactivity of a uranium(vi) carbene imido oxo complex
topic carbene ligands; imido ligands; multiple bonding; oxo ligands; uranium
url https://eprints.nottingham.ac.uk/46639/
https://eprints.nottingham.ac.uk/46639/
https://eprints.nottingham.ac.uk/46639/