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Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex**

We report the uranium(VI) carbene imido oxo complex [U(BIPM(TMS))(NMes)(O)(DMAP)(2)] (5, BIPM(TMS)=C(PPh(2)NSiMe(3))(2); Mes=2,4,6-Me(3)C(6)H(2); DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordin...

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Autores principales: Lu, Erli, Cooper, Oliver J, McMaster, Jonathan, Tuna, Floriana, McInnes, Eric J L, Lewis, William, Blake, Alexander J, Liddle, Stephen T
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY-VCH Verlag 2014
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4464547/
https://www.ncbi.nlm.nih.gov/pubmed/24842784
http://dx.doi.org/10.1002/anie.201403892
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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
collection PubMed
description We report the uranium(VI) carbene imido oxo complex [U(BIPM(TMS))(NMes)(O)(DMAP)(2)] (5, BIPM(TMS)=C(PPh(2)NSiMe(3))(2); Mes=2,4,6-Me(3)C(6)H(2); 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(BIPM(TMS))(O)(2)(DMAP)(2)] (6).
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spelling pubmed-44645472015-06-17 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 Angew Chem Int Ed Engl Communications We report the uranium(VI) carbene imido oxo complex [U(BIPM(TMS))(NMes)(O)(DMAP)(2)] (5, BIPM(TMS)=C(PPh(2)NSiMe(3))(2); Mes=2,4,6-Me(3)C(6)H(2); 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(BIPM(TMS))(O)(2)(DMAP)(2)] (6). WILEY-VCH Verlag 2014-06-23 2014-05-19 /pmc/articles/PMC4464547/ /pubmed/24842784 http://dx.doi.org/10.1002/anie.201403892 Text en © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. http://creativecommons.org/licenses/by/3.0/ This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
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 Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4464547/
https://www.ncbi.nlm.nih.gov/pubmed/24842784
http://dx.doi.org/10.1002/anie.201403892
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