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Sodium decavanadate

Sodium decavanadate describes any member of the family of inorganic compounds with the formula Na<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>]·nH<sub>2</sub>O. These are sodium salts of the orange-colored decavanadate anion [V<sub>10</sub>O<sub>28</sub>]<sup>6−</sup>. Numerous other decavanadate salts have been isolated and studied since 1956 when it was first characterized.

Acid-base properties

Aqueous vanadate (V) compounds undergo various self-condensation reactions. Depending on pH, major vanadate anions in solution include , , , , , and . The anions often reversibly protonate. Decavanadate forms according to this equilibrium:

The structure of the various protonation states of the decavanadate ion has been examined by <sup>51</sup>V NMR spectroscopy. Each species gives three signals; with slightly varying chemical shifts around −425, −506, and −523&nbsp;ppm relative to vanadium oxytrichloride; suggesting that rapid proton exchange occurs resulting in equally symmetric species. The three protonations of decavanadate have been shown to occur at the bridging oxygen centers, indicated as B and C in figure 1.

Decavanadate is most stable in the pH&nbsp;4–7 region. Solutions of vanadate turn bright orange at pH&nbsp;6.5, indicating the presence of decavanadate. Other vanadates are colorless. Below pH&nbsp;2.0, brown V<sub>2</sub>O<sub>5</sub> precipitates as the hydrate.

Structure

The decavanadate ion consists of ten fused VO<sub>6</sub> octahedra and has D<sub>2h</sub> symmetry. The structure of Na<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>]·18H<sub>2</sub>O has been confirmed with X-ray crystallography.

The decavanadate anions contains three sets of equivalent V atoms (see fig. 1). These include two central VO<sub>6</sub> octahedra (V<sub>c</sub>) and four each peripheral tetragonal-pyramidal VO<sub>5</sub> groups (V<sub>a</sub> and V<sub>b</sub>). 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.

The oxidation state of vanadium in decavanadate is +5.

Preparation

The preparation of decavanadate is achieved by acidifying an aqueous solution of orthovanadate (:

The formation of decavanadate is optimized by maintaining a pH range of 4–7. Typical side products include metavanadate, , and hexavanadate, , ions.

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.

Related decavanadates

Many decavanadate salts have been characterized. , Ca<sup>2+</sup>, Ba<sup>2+</sup>, Sr<sup>2+</sup>, and group I decavanadate salts are prepared by the acid–base reaction between V<sub>2</sub>O<sub>5</sub> and the oxide, hydroxide, carbonate, or hydrogen carbonate of the desired positive ion.

Other decavanadates:

(NH<sub>4</sub>)<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>]·6H<sub>2</sub>O
K<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>]·9H<sub>2</sub>O
K<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>]·10H<sub>2</sub>O
Ca<sub>3</sub>[V<sub>10</sub>O<sub>28</sub>]·16H<sub>2</sub>O
K<sub>2</sub>Mg<sub>2</sub>[V<sub>10</sub>O<sub>28</sub>]·16H<sub>2</sub>O
K<sub>2</sub>Zn<sub>2</sub>[V<sub>10</sub>O<sub>28</sub>]·16H<sub>2</sub>O
Cs<sub>2</sub>Mg<sub>2</sub>[V<sub>10</sub>O<sub>28</sub>]·16H<sub>2</sub>O
Cs<sub>4</sub>Na<sub>2</sub>[V<sub>10</sub>O<sub>28</sub>]·10H<sub>2</sub>O
K<sub>4</sub>Na<sub>2</sub>[V<sub>10</sub>O<sub>28</sub>]·16H<sub>2</sub>O
Sr<sub>3</sub>[V<sub>10</sub>O<sub>28</sub>]·22H<sub>2</sub>O
Ba<sub>3</sub>[V<sub>10</sub>O<sub>28</sub>]·19H<sub>2</sub>O
[(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub>P]H<sub>3</sub>V<sub>10</sub>O<sub>28</sub>·4CH<sub>3</sub>CN
Ag<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>]·4H<sub>2</sub>O

Naturally occurring decavanadates include:

Ca<sub>3</sub>V<sub>10</sub>O<sub>28</sub>·17H<sub>2</sub>O (Pascoite)
Ca<sub>2</sub>Mg(V<sub>10</sub>O<sub>28</sub>)·16H<sub>2</sub>O (Magnesiopascoite)
Na<sub>4</sub>Mg(V<sub>10</sub>O<sub>28</sub>)·24H<sub>2</sub>O (Huemulite)

References