Abstract
(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); together the experimental and theoretical data reproduce the experimental outcomes and suggest that 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. This work highlights that caution is warranted utilising CS2 as a reactivity surrogate for CO2.
Original language | English |
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Journal | Chemistry: A European Journal |
Volume | 23 |
Issue number | 12 |
Early online date | 30 Jan 2017 |
DOIs | |
Publication status | Published - 2017 |
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CCDC 1486565: Experimental Crystal Structure Determination
Cleaves, P. (Contributor), Kefalidis, C. E. (Contributor), Gardner, B. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), Lewis, W. (Contributor), Maron, L. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lwwq2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lwwq2&sid=DataCite
Dataset
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CCDC 1486563: Experimental Crystal Structure Determination
Cleaves, P. (Contributor), Kefalidis, C. E. (Contributor), Gardner, B. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), Lewis, W. (Contributor), Maron, L. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lwwn0, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lwwn0&sid=DataCite
Dataset
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CCDC 1486564: Experimental Crystal Structure Determination
Cleaves, P. (Contributor), Kefalidis, C. E. (Contributor), Gardner, B. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), Lewis, W. (Contributor), Maron, L. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lwwp1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lwwp1&sid=DataCite
Dataset