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

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(Tren^TIPS )(N)][K(B15C5)₂ ] (1, Tren^TIPS =N(CH₂ CH₂ NSiiPr₃ )₃ ; B15C5=benzo-15-crown-5) reacts with CO₂ to give [U(Tren^TIPS )(O)(NCO)][K(B15C5)₂ ] (3), whereas the uranium(VI) nitride [U(Tren^TIPS )(N)] (2) reacts with CO₂ to give isolable [U(Tren^TIPS )(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren^TIPS )(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(Tren^TIPS )(κ² -CS₃ )][K(B15C5)₂ ] (6), 2, and [K(B15C5)₂ ][NCS] (7), whereas 2 reacts with CS₂ to give [U(Tren^TIPS )(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 .

Keywords: carbon dioxide; carbon disulfide; density functional theory; nitride; uranium.