Sodium decavanadate describes any member of the family of inorganic compounds with the formula Na6[V10O28](H2O)n. These are sodium salts of the orange-colored decavanadate anion [V10O28]6−.[1] Numerous other decavanadate salts have been isolated and studied since 1956 when it was first characterized.[2]
Preparation
The preparation of decavanadate is achieved by acidifying an aqueous solution of ortho-vanadate:[1]
The formation of decavanadate is optimized by maintaining a pH range of 4–7. Typical side products include metavanadate, [VO3]−, and hexavanadate, [V6O16]2−, ions.[1]
Structure
The decavanadate ion consists of 10 fused VO6 octahedra and has D2h symmetry.[3][4][5] The structure of Na6[V10O28]·18H2O has been confirmed with X-ray crystallography.[6]
Figure 1: structure of decavanadate ion with equivalent V and O atoms indicated
The decavanadate anions contains three sets of equivalent V atoms (see fig. 1).[3] These include two central VO6 octahedra (Vc) and four each peripheral tetragonal-pyramidal VO5 groups (Va and Vb). There are seven unique groups of oxygen atoms (labeled A through G). Two of these (A) bridge to six V centers, four (B) bridge three V centers, fourteen of these (C, D and E) span edges between pairs of V centers, and eight (F and G) are peripheral.
Aqueous vanadate (V) compounds undergo various self-condensation reactions.[7] Depending on pH, major vanadate anions in solution include VO2(H2O)42+, VO43−, V2O73−, V3O93−, V4O124−, and V10O286−. The anions often reversibly protonate.[5] Decavanadate forms according to this equilibrium:[2][7]
H3V10O283− ⇌ H2V10O284− + H+
H2V10O284− ⇌ HV10O285− + H+
HV10O285−(aq) ⇌ V10O286− + H+
The structure of the various protonation states of the decavanadate ion has been examined by 51V NMR spectroscopy.[5][7] Each species gives three signals; with slightly varying chemical shifts around −425, −506, and −523 ppm relative to vanadium oxytrichloride; suggesting that rapid proton exchange occurs resulting in equally symmetric species.[8] The three protonations of decavanadate have been shown to occur at the bridging oxygen centers, indicated as B and C in figure 1.[8]
Decavanadate is most stable in pH 4–7 region.[1][4][7] Solutions of vanadate turn bright orange at pH 6.5, indicating the presence of decavanadate. Other vanadates are colorless. Below pH 2.0, brown V2O5 precipitates as the hydrate.[3][7]
V10O286− + 6H+ + 12H2 ⇌ 5V2O5
Potential uses
Decavanadate has been found to inhibit phosphoglycerate mutase, an enzyme which catalyzes step 8 of glycolysis. In addition, decavandate was found to have modest inhibition of Leishmania tarentolae viability, suggesting that decavandate may have a potential use as a topical inhibitor of protozoan parasites.[9]
Related decavanadates
Many decavanadate salts have been characterized. NH4+, Ca2+, Ba2+, Sr2+, and group I decavanadate salts are prepared by the acid-base reaction between V2O5 and the oxide, hydroxide, carbonate, or hydrogen carbonate of the desired positive ion.[1]
^ abcdefghEvans, H. T. Jr (1966). "The molecular structure of the isopoly complex ion, decavanadate". Inorg. Chem. 5: 967–977. doi:10.1021/ic50040a004.
^ abKustin, K.; Pessoa, J. C.; Crans, D. C. (2007). Vandadium: The Versatile Metal. Washington, D. C.: American Chemical Society. ISBN978-0-8412-7446-4.
^ abcRehder, D. (2008). Bioinorganic Vanadium Chemistry. Wiley & Sons. pp. 13–51. ISBN978-0-470-06509-9.
^ abcdeTracey, A.S.; Crans, D.C. (1998). Vanadium Compounds. Washington D.C.: American Chemical Society. ISBN0-8412-3589-9.
^ abcDay, V. W.; Klemperer, W. G.; Maltbie, D. J. (1987). "Where Are the Protons in H3V10O283−?". Journal of the American Chemical Society. 109 (10): 2991–3002. doi:10.1021/ja00244a022.
^ abcDametto, A.C.; de Arauju, A.S.; de Souza Correa, R.; Guilherme, L.R.; Massabni, A.C. (2010). "Synthesis, infrared spectroscopy and crystal structure determination of a new decavanadate". J Chem Crystallogr. 40 (11): 897–901. doi:10.1007/s10870-010-9759-x. S2CID97736357.
