Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations.

Six new anionic bismuth-oxido clusters containing trifluoroacetate ligands were prepared. These include two new BiO clusters: [M(NCMe)(HO)][Bi(μ-O)(μ-OH)(CFCO)] with an octahedral BiO(OH) core (M = Ni, 1a; Co, 1b) and four BiO clusters, {[Co(NCMe)][Bi(μ-O)(CFCO)]} (2a), {[Co{HC(MeCO)(MeCNH)}][Bi(μ-O)(CFCO)]·2[CFCO]·2[CFCOH]·2[HO]} (2b), {[Cu(NCMe)][Bi(μ-O)(CFCO)]·2[CFCOH]} (2c), and {[MeN][Bi(μ-O)(CFCO)]·2[CFCOH]} (2d). These are among the first bismuth-oxido anionic clusters synthesized, and the first to have transition metal countercations. The BiO anion in 1a and 1b is a high-symmetry octahedron. Additionally, two of the new BiO clusters are arranged in 1D polymeric structures via bridging carboxylate ligands. The cation in compound 2c had not been previously characterized and was also observed in the synthesis of [Co{HC(MeCO)(MeCNH)}][Bi(NO)] (3). The new compounds were characterized using single crystal X-ray crystallography and elemental analysis.