Anionic Bismuth-Oxido Carboxylate Clusters with Transition Metal Countercations

Six new anionic bismuth-oxido clusters containing trifluoroacetate ligands were prepared. These include two new Bi 6 O 8 clusters: [M(NCMe) 2 (H 2 O) 4 ] 3 [Bi 6 (μ 3 -O) 4 (μ 3 -OH) 4 (CF 3 CO 2 ) 12 ] with an octahedral Bi 6 O 4 (OH) 4 core (M = Ni, 1a; Co, 1b) and four Bi 4 O 2 clusters, {[Co(NCMe) 6 ][Bi 4 (μ 3 -O) 2 (CF 3 CO 2 ) 10 ]} n (2a), {[Co{HC(MeCO) 2 (MeCNH)} 2 ][Bi 4 (μ 3 -O) 2 (CF 3 CO 2 ) 10 ]·2[CF 3 CO 2 ]·2[CF 3 CO 2 H]·2[H 2 O]} n (2b), {[Cu(NCMe) 4 ] 2 [Bi 4 (μ 3 -O) 2 (CF 3 CO 2 ) 10 ]·2[CF 3 CO 2 H]} n (2c), and {[Me 4 N] 2 [Bi 4 (μ 3 -O) 2 (CF 3 CO 2 ) 10 ]·2[CF 3 CO 2 H]} n (2d). These are among the first bismuth-oxido anionic clusters synthesized, and the first to have transition metal countercations. The Bi 6 O 8 anion in 1a and 1b is a high-symmetry octahedron. Additionally, two of the new Bi 4 O 2 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) 2 (MeCNH)} 2 ][Bi(NO 3 ) 6 ] (3). The new compounds were characterized using single crystal X-ray crystallography and elemental analysis.