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.