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Sodium decavanadate

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Sodium decavanadate
Identifiers
3D model ( JSmol )
ChemSpider
EC Number
  • (anhydrous): 235-375-1
  • InChI=1S/6Na.28O.10V/q6*+1;28*-2;10*+5
    Key: WSNCYQDYQWKFLZ-UHFFFAOYSA-N
  • (anhydrous): [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[V].[V].[V].[V].[V].[V].[V].[V].[V].[V]
Properties
Na 6 [V 10 O 28 ]
Molar mass 1419.6 g/mol
Appearance orange solid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N  ( what is   checkY ☒N  ?)

Sodium decavanadate describes any member of the family of inorganic compounds with the formula Na 6 [V 10 O 28 ](H 2 O) n . These are sodium salts of the orange-colored decavanadate anion [V 10 O 28 ] 6? . [1] Numerous other decavanadate salts have been isolated and studied since 1956 when it was first characterized. [2]

Preparation [ edit ]

The preparation of decavanadate is achieved by acidifying an aqueous solution of ortho- vanadate : [1]

10 Na 3 [VO 4 ] + 24 HOAc → Na 6 [V 10 O 28 ] + 12 H 2 O + 24 NaOAc

The formation of decavanadate is optimized by maintaining a pH range of 4?7. Typical side products include metavanadate, [VO 3 ] ? , and hexavanadate, [V 6 O 16 ] 2? , ions. [1]

Structure [ edit ]

The decavanadate ion consists of 10 fused VO 6 octahedra and has D 2h symmetry. [3] [4] [5] The structure of Na 6 [V 10 O 28 ]·18H 2 O 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 VO 6 octahedra (V c ) and four each peripheral tetragonal-pyramidal VO 5 groups (V a and V b ). 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.

Acid-base properties [ edit ]

Aqueous vanadate (V) compounds undergo various self-condensation reactions. [7] Depending on pH, major vanadate anions in solution include VO 2 (H 2 O) 4 2+ , VO 4 3? , V 2 O 7 3? , V 3 O 9 3? , V 4 O 12 4? , and V 10 O 28 6? . The anions often reversibly protonate . [5] Decavanadate forms according to this equilibrium: [2] [7]

H 3 V 10 O 28 3? ? H 2 V 10 O 28 4? + H +
H 2 V 10 O 28 4? ? HV 10 O 28 5? + H +
HV 10 O 28 5? (aq) ? V 10 O 28 6? + H +

The structure of the various protonation states of the decavanadate ion has been examined by 51 V 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 V 2 O 5 precipitates as the hydrate. [3] [7]

V 10 O 28 6? + 6H + + 12H 2 ? 5V 2 O 5

Potential uses [ edit ]

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 [ edit ]

Many decavanadate salts have been characterized. NH 4 + , Ca 2+ , Ba 2+ , Sr 2+ , and group I decavanadate salts are prepared by the acid-base reaction between V 2 O 5 and the oxide, hydroxide, carbonate, or hydrogen carbonate of the desired positive ion. [1]

6 NH 3 + 5 V 2 O 5 + 3 H 2 O ? (NH 4 ) 6 [V 10 O 28 ]

Other decavanadates:

(NH 4 ) 6 [V 10 O 28 ]·6H 2 O [2]
K 6 [V 10 O 28 ]·9H 2 O [2]
K 6 [V 10 O 28 ]·10H 2 O [1] [2] [3]
Ca 3 [V 10 O 28 ]·16H 2 O [2] [3]
K 2 Mg 2 [V 10 O 28 ]·16H 2 O [2] [3]
K 2 Zn 2 [V 10 O 28 ]·16H 2 O [1] [2] [3]
Cs 2 Mg 2 [V 10 O 28 ]·16H 2 O [3]
Cs 4 Na 2 [V 10 O 28 ]·10H 2 O [10]
K 4 Na 2 [V 10 O 28 ]·16H 2 O [11]
Sr 3 [V 10 O 28 ]·22H 2 O [10]
Ba 3 [V 10 O 28 ]·19H 2 O [10]
[(C 6 H 5 ) 4 P]H 3 V 10 O 28 ·4CH 3 CN [8]
Ag 6 [V 10 O 28 ]·4H 2 O [12] [13]

Naturally occurring decavanadates include:

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

References [ edit ]

  1. ^ a b c d e f g Johnson, G.; Murmann, R. K. (1979). "Sodium and Ammonium Decayanadates(V)". Inorganic Syntheses . Vol. 19. pp. 140?145. doi : 10.1002/9780470132500.ch32 . ISBN   978-0-471-04542-7 .
  2. ^ a b c d e f g h Rossotti, F. J.; Rossotti, H. (1956). "Equilibrium Studies of Polyanions" . Acta Chemica Scandinavica . 10 : 957?984. doi : 10.3891/acta.chem.scand.10-0957 .
  3. ^ a b c d e f g h Evans, H. T. Jr (1966). "The molecular structure of the isopoly complex ion, decavanadate". Inorg. Chem . 5 : 967?977. doi : 10.1021/ic50040a004 .
  4. ^ a b Kustin, K.; Pessoa, J. C.; Crans, D. C. (2007). Vandadium: The Versatile Metal . Washington, D. C.: American Chemical Society. ISBN   978-0-8412-7446-4 .
  5. ^ a b c Rehder, D. (2008). Bioinorganic Vanadium Chemistry . Wiley & Sons. pp. 13?51. ISBN   978-0-470-06509-9 .
  6. ^ Durif, P.A.; Averbuch-pouchot, M.T. (1980). "Structure d'un Decavanadate d'Hexasodium Hydrate". Acta Crystallogr. B . 36 (3): 680?682. Bibcode : 1980AcCrB..36..680D . doi : 10.1107/S0567740880004116 .
  7. ^ a b c d e Tracey, A.S.; Crans, D.C. (1998). Vanadium Compounds . Washington D.C.: American Chemical Society. ISBN   0-8412-3589-9 .
  8. ^ a b c Day, V. W.; Klemperer, W. G.; Maltbie, D. J. (1987). "Where Are the Protons in H 3 V 10 O 28 3? ?". Journal of the American Chemical Society . 109 (10): 2991?3002. doi : 10.1021/ja00244a022 .
  9. ^ Turner, Timothy; Nguyen, Victoria; McLauchlan, Craig; Dymon, Zaneta; Dorsey, Benjamin; Hooker, Jaqueline; Jones, Marjorie (March 2012). "Inhibitory effects of decavanadate on several enzymes and Leishmania tarentolae In Vitro" . Journal of Inorganic Biochemistry . 108 : 96?104. doi : 10.1016/j.jinorgbio.2011.09.009 . PMID   22005446 . Retrieved 23 January 2021 .
  10. ^ a b c Dametto, 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 . S2CID   97736357 .
  11. ^ Matias, P.M.; Pessoa, J.C.; Duarte, M.T.; Maderia, C. (2000). "Tetrapotassium disodium decavanadate(V) decahydrate". Acta Crystallogr. C . 57 (3): e75?e76. Bibcode : 2000AcCrC..56E..75M . doi : 10.1107/S0108270100001530 . PMID   15263200 .
  12. ^ Escobar, M.E.; Baran, E.J. (1981). "Die Schwingungsspektren einiger kristalliner Dekavanadate" . Monatshefte fur Chemie . 112 : 43?49. doi : 10.1007/BF00906241 . S2CID   101366009 .
  13. ^ Aureliano, Manuel; Crans, Debbie C. (2009). "Decavanadate ( V
    10     O 6?
    28     ) and oxovanadates: Oxometalates with many biological activities"     . Journal of Inorganic Biochemistry . 103 (4): 536?546. doi : 10.1016/j.jinorgbio.2008.11.010 . ISSN   0162-0134 . PMID   19110314 .
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