Uranium Cyanides from Reactions in Liquid Ammonia Solution.

Reactions of uranium tri‐ and tetrahalides, UBr3, UI3, UCl4, and UI4, with different cyanides MCN (M=K, Ag) in liquid anhydrous ammonia led to three novel uranium(IV) cyanide compounds. The reaction of UCl4 in the presence of KCN resulted in the compound [U(CN)(NH3)8]Cl3 ⋅ 3NH3, while UBr3 and UI3 were oxidized in the presence of AgCN to form the compounds ∞1[ ${{}_{\infty }{}^{1}[}$ (μ‐CN){(H3N)5U(μ‐NH2)3U(NH3)5}]Br4 ⋅ 2NH3, and ∞1[ ${{}_{\infty }{}^{1}[}$ (μ‐CN){(H3N)5U(μ‐NH2)3U(NH3)5}]I4 ⋅ 2NH3. The reaction of UI4 with KCN in aNH3 also yielded the compound ∞1[ ${{}_{\infty }{}^{1}[}$ (μ‐CN){(H3N)5U(μ‐NH2)3U(NH3)5}]I4 ⋅ 2NH3. The compounds ∞1[ ${{}_{\infty }{}^{1}[}$ (μ‐CN){(H3N)5U(μ‐NH2)3U(NH3)5}]X4 ⋅ 2NH3 (X=Br, I) crystallize in different space groups, Pmn21 (no. 31) and Imm2 (no. 44), respectively. In both cases, the ∞1[ ${{}_{\infty }{}^{1}[}$ (μ‐CN){(H3N)5U(μ‐NH2)3U(NH3)5}]4+ cation forms infinite strands. We conducted quantum‐chemical calculations and Intrinsic Bond Orbital analyses on the observed [U(CN)(NH3)8]3+ cation and the [(μ‐CN)2{(H3N)5U(μ‐NH2)3U(NH3)5}]3+ model cation to gain insight into the bonding situation. [ABSTRACT FROM AUTHOR]