Reactivity of a triamidoamine terminal uranium(VI)-nitride with 3d-transition metal metallocenes.

Reactions between [(Tren)UN] (1, Tren = {N(CHCHNSiPr)}) and [M(η-CR)] (M/R = Cr/H, Mn/H, Fe/H, Ni/H) were intractable, but M/R = Co/H or Co/Me afforded [(Tren)UN-(η:η-CH)Co(η-CH)] (2) and [(Tren)U-NH] (3), respectively. For M/R = V/H [(Tren)U-NV(η-CH)] (4), was isolated. Complexes 2-4 evidence one-/two-electron uranium reductions, nucleophilic nitrides, and partial N-atom transfer.

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 CE (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 )(N)][K(B15C5) ] (1, Tren =N(CH CH NSiiPr ) ; B15C5=benzo-15-crown-5) reacts with CO to give [U(Tren )(O)(NCO)][K(B15C5) ] (3), whereas the uranium(VI) nitride [U(Tren )(N)] (2) reacts with CO to give isolable [U(Tren )(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren )(O)] (5) with concomitant formation of N and CO proposed, with the latter trapped as a vanadocene adduct.

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes.

Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin-orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides.

Two-electron reductive carbonylation of terminal uranium(V) and uranium(VI) nitrides to cyanate by carbon monoxide.

Two-electron reductive carbonylation of the uranium(VI) nitride [U(Tren(TIPS))(N)] (2, Tren(TIPS)=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(Tren(TIPS))(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(Tren(TIPS))] (4) and KNCO, or cyanate retention in [U(Tren(TIPS))(NCO)][K(B15C5)2] (5, B15C5=benzo-15-crown-5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared from CO and the uranium(V) nitride [{U(Tren(TIPS))(N)K}2] (6), with or without B15C5, respectively.