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      Terminal Uranium(V/VI) Nitride Activation of Carbon Dioxide and Carbon Disulfide: Factors Governing Diverse and Well-Defined Cleavage and Redox Reactions.

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          Abstract

          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(CH2 CH2 NSiiPr3 )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 Ph3 PS. 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 .

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          Author and article information

          Journal
          Chemistry
          Chemistry (Weinheim an der Bergstrasse, Germany)
          Wiley-Blackwell
          1521-3765
          0947-6539
          Feb 24 2017
          : 23
          : 12
          Affiliations
          [1 ] School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
          [2 ] LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, Toulouse, 31077, France.
          [3 ] School of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
          [4 ] School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
          Article
          10.1002/chem.201605620
          28075505
          fb6d22ae-c4d0-4d9a-a58b-e76cd60f8611
          History

          carbon dioxide,carbon disulfide,density functional theory,nitride,uranium

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