Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions
The reactivity of terminal uranium(V/VI) nitrides with CE2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(TrenTIPS)(N)][K(B15C5)2] (1, TrenTIPS=N(CH2CH2NSiiPr3)3; B15C5=benzo-15-crown-5) reacts with CO2 t...
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| Format: | Article |
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Wiley-VCH Verlag
2017
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| Online Access: | https://eprints.nottingham.ac.uk/46648/ |
| _version_ | 1848797376950566912 |
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| author | Cleaves, Peter A. Kefalidis, Christos E. Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. Lewis, William Maron, Laurent Liddle, Stephen T. |
| author_facet | Cleaves, Peter A. Kefalidis, Christos E. Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. Lewis, William Maron, Laurent Liddle, Stephen T. |
| author_sort | Cleaves, Peter A. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The reactivity of terminal uranium(V/VI) nitrides with CE2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(TrenTIPS)(N)][K(B15C5)2] (1, TrenTIPS=N(CH2CH2NSiiPr3)3; B15C5=benzo-15-crown-5) reacts with CO2 to give [U(TrenTIPS)(O)(NCO)][K(B15C5)2] (3), whereas the uranium(VI) nitride [U(TrenTIPS)(N)] (2) reacts with CO2 to give isolable [U(TrenTIPS)(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(TrenTIPS)(O)] (5) with concomitant formation of N2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS2 to give [U(TrenTIPS)(κ2-CS3)][K(B15C5)2] (6), 2, and [K(B15C5)2][NCS] (7), whereas 2 reacts with CS2 to give [U(TrenTIPS)(NCS)] (8) and “S”, with the latter trapped as Ph3PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS2 as a reactivity surrogate for CO2. |
| first_indexed | 2025-11-14T20:02:54Z |
| format | Article |
| id | nottingham-46648 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:02:54Z |
| publishDate | 2017 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-466482020-05-04T18:33:37Z https://eprints.nottingham.ac.uk/46648/ Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions Cleaves, Peter A. Kefalidis, Christos E. Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. Lewis, William Maron, Laurent Liddle, Stephen T. The reactivity of terminal uranium(V/VI) nitrides with CE2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(TrenTIPS)(N)][K(B15C5)2] (1, TrenTIPS=N(CH2CH2NSiiPr3)3; B15C5=benzo-15-crown-5) reacts with CO2 to give [U(TrenTIPS)(O)(NCO)][K(B15C5)2] (3), whereas the uranium(VI) nitride [U(TrenTIPS)(N)] (2) reacts with CO2 to give isolable [U(TrenTIPS)(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(TrenTIPS)(O)] (5) with concomitant formation of N2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS2 to give [U(TrenTIPS)(κ2-CS3)][K(B15C5)2] (6), 2, and [K(B15C5)2][NCS] (7), whereas 2 reacts with CS2 to give [U(TrenTIPS)(NCS)] (8) and “S”, with the latter trapped as Ph3PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS2 as a reactivity surrogate for CO2. Wiley-VCH Verlag 2017-02-24 Article PeerReviewed Cleaves, Peter A., Kefalidis, Christos E., Gardner, Benedict M., Tuna, Floriana, McInnes, Eric J.L., Lewis, William, Maron, Laurent and Liddle, Stephen T. (2017) Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions. Chemistry - a European Journal, 23 (12). pp. 2950-2959. ISSN 1521-3765 carbon dioxide; carbon disulfide; density functional theory; nitride; uranium http://onlinelibrary.wiley.com/doi/10.1002/chem.201605620/abstract doi:10.1002/chem.201605620 doi:10.1002/chem.201605620 |
| spellingShingle | carbon dioxide; carbon disulfide; density functional theory; nitride; uranium Cleaves, Peter A. Kefalidis, Christos E. Gardner, Benedict M. Tuna, Floriana McInnes, Eric J.L. Lewis, William Maron, Laurent Liddle, Stephen T. Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| title | Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| title_full | Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| title_fullStr | Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| title_full_unstemmed | Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| title_short | Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| title_sort | terminal uranium(v/vi) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions |
| topic | carbon dioxide; carbon disulfide; density functional theory; nitride; uranium |
| url | https://eprints.nottingham.ac.uk/46648/ https://eprints.nottingham.ac.uk/46648/ https://eprints.nottingham.ac.uk/46648/ |