Studies on the Hydrolysis of Metal Ions. 23. Hydrolysis of the Ion Bi6(OH)6+12 in Perchlorate Medium.

Solvolytic routes to new nonabismuth hydroxy- and alkoxy-oxo complexes: synthesis, characterization and solid-state structures of novel nonabismuth polyoxo cations Bi9(µ3-O)8(µ3-OR)65+(R = H, Et)

“…1), similar to other Bi n complexes. 1,13,[22][23][24] The three peripheral Bi atoms are tetracoordinate, similar to that in [Bi 6 (m 3 -O) 4 (m 3 -OH) 4 ]X 6 (X 5 ClO 4 , NO 3 ) 13,24,25 . There is considerable debate 28 about metal-metal interactions in polyoxo clusters of the heavy main-group elements.…”

“…Despite solution evidence for polyoxo Bi n complexes with nuclearities n 5 2-9, [12][13][14][15][16] only octahedral Bi 6 (m 3 -O) x (m 3 -OH) 82x (102x)+ salts have been isolated. Nonabismuth complexes are postulated hydrolysis products based on electrophoresis and tyndallometry.…”

“…Nonabismuth complexes are postulated hydrolysis products based on electrophoresis and tyndallometry. 12,13,16 The paucity of structural information stems from the high Lewis acidity of Bi(III), expandable coordination sphere, and low aqueous solubility of its salts. 17,18 Intractable oligomers are often obtained, and isolation conditions are not well established.…”

Measurements and Modeling To Determine the Reduction Potential of Uncomplexed Bi(III) in Nitrate Solutions for Application in Bi(III)-Ligand Equilibria Studies by Voltammetry

“…. 8,14,18 Other mononuclear species were also found in more dilute solutions and Bidleman 19 determined formation constants for BiOH 2+ , Bi(OH) 3 , and Bi(OH) 4 − (for Bi(III) < 10 −4 M). The Bi(OH) 2 + species was initially not detected, and it was suggested that the stoichiometrically equivalent hexamer is much more stable than this species.…”

“…Bi­(III) hydrolysis, however, has been extensively studied and was instrumental in developing techniques to investigate hydrolysis of metal ions in general . The formation of the Bi­(OH) 2+ species was confirmed early on. − There was also indication of the formation of bismuth polynuclear species with much debate as to the exact stoichiometry of these species. − Evidence from various techniques supported the presence of the hexamer, Bi 6 (OH) 12 6+ , as the dominant species under the specific experimental conditions. ,,− This species could also be referred to as Bi 6 O 6 6+ because numerous techniques have difficulty in differentiating whether O 2 – or OH – is bound to the metal ion . It was also recognized that the hexameric species was in equilibrium with even larger complexes proposed to be Bi 9 (OH) 20 7+ , Bi 9 (OH) 21 6+ , and Bi 9 (OH) 22 5+ . ,, …”