関: metavanadate、orthovanadate、sodium vanadate、vanadate、vanadyl

WordNet

a salt or ester of vanadic acid; an anion containing pentavalent vanadium

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2020/04/18 01:07:29」(JST)

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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]

10 Na₃[VO₄] + 24 HOAc → Na₆[V₁₀O₂₈] + 12 H₂O + 24 NaOAc

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 D_2h 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 (V_c) and four each peripheral tetragonal-pyramidal VO₅ 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

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 V₁₀O₂₆⁶⁻. 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

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]

6 NH₃ + 5 V₂O₅ + 3 H₂O ⇌ (NH₄)₆[V₁₀O₂₈]

Other decavanadates:

(NH₄)₆[V₁₀O₂₈]·6H₂O^[2]

K₆[V₁₀O₂₈]·9H₂O^[2]

K₆[V₁₀O₂₈]·10H₂O^[1]^[2]^[3]

Ca₃[V₁₀O₂₈]·16H₂O^[2]^[3]

K₂Mg₂[V₁₀O₂₈]·16H₂O^[2]^[3]

K₂Zn₂[V₁₀O₂₈]·16H₂O^[1]^[2]^[3]

Cs₂Mg₂[V₁₀O₂₈]·16H₂O^[3]

Cs₄Na₂[V₁₀O₂₈]·10H₂O^[9]

K₄Na₂[V₁₀O₂₈]·16H₂O^[10]

Sr₃[V₁₀O₂₈]·22H₂O^[9]

Ba₃[V₁₀O₂₈]·19H₂O^[9]

[(C₆H₅)₄P]H₃V₁₀O₂₈·4CH₃CN^[8]

Ag₆[V₁₀O₂₈]·4H₂O^[11]

^ Aureliano, Manuel; Crans, Debbie C. (2009). "Decavanadate and oxovanadates: Oxometalates with many biological activities". Journal Inorganic Biochemistry 103: 536–546. doi:10.1016/j.jinorgbio.2008.11010. Naturally occurring dewcavanadates include:

Ca₃V₁₀O₂₈·17 H₂O (Pascoite)

Ca₂Mg(V₁₀O₂₈)·16H₂O (Magnesiopascoite)

Na₄Mg(V₁₀O₂₈)·24H₂O (Huemulite)

References

^ ^a ^b ^c ^d ^e ^f ^g Johnson, G.; Murmann, R. K. (2007). Sodium and Ammonium Decavanadates. Inorganic Syntheses. 19. pp. 140–145. doi:10.1002/9780470132500.ch32.CS1 maint: uses authors parameter (link)
^ ^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.CS1 maint: uses authors parameter (link)
^ ^a ^b ^c ^d ^e ^f ^g ^h Evans Jr., H. T. (1966). "The molecular structure of the isopoly complex ion, decavanadate". Inorg. Chem. 5: 967–977. doi:10.1021/ic50040a004.CS1 maint: uses authors parameter (link)
^ ^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.CS1 maint: uses authors parameter (link)
^ ^a ^b ^c Rehder, D. (2008). Bioinorganic Vanadium Chemistry. Wiley & Sons. pp. 13–51. ISBN 978-0-470-06509-9.CS1 maint: uses authors parameter (link)
^ Durif, P.A.; Averbuch-pouchot, M.T. (1980). "Structure d'un Décavanadate d'Hexasodium Hydraté". Acta Crystallogr. B. 36 (3): 680–682. doi:10.1107/S0567740880004116.CS1 maint: uses authors parameter (link)
^ ^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.
^ ^a ^b ^c Day, 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.CS1 maint: uses authors parameter (link)
^ ^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.CS1 maint: uses authors parameter (link)
^ Matias, P.M.; Pessoa, J.C.; Duarte, M.T.; Maderia, C. (2000). "Tetrapotassium disodium decavanadate(V) decahydrate". Acta Crystallogr. C. 57 (3): e75–e76. doi:10.1107/S0108270100001530. PMID 15263200.CS1 maint: uses authors parameter (link)
^ Escobar, M.E.; Baran, E.J. (1981). "Die Schwingungsspektren einiger kristalliner Dekavanadate". Monatshefte für Chemie. 112: 43–49. doi:10.1007/BF00906241.CS1 maint: uses authors parameter (link)

English Journal

TiO2/vanadate (Sr10V6O25, Ni3V2O8, Zn2V2O7) heterostructured photocatalysts with enhanced photocatalytic activity for photoreduction of CO2 into CH4.

Yan Y1, Yu Y2, Wu D1, Yang Y1, Cao Y1.
Nanoscale.Nanoscale.2015 Dec 23;8(2):949-58. doi: 10.1039/c5nr05332c.
A series of TiO2/vanadate (Sr10V6O25, Ni3V2O8, Zn2V2O7) heterostructured photocatalysts were prepared by a simple sol-gel method. The theoretical calculations imply the possible energy band match between TiO2 and vanadates. Characterized by XRD, Raman, TEM, EDX, XPS, absorption spectra, PL and time-
PMID 26662343

Antidiabetic, Chemical, and Physical Properties of Organic Vanadates as Presumed Transition-State Inhibitors for Phosphatases.

Crans DC1.
The Journal of organic chemistry.J Org Chem.2015 Dec 18;80(24):11899-915. doi: 10.1021/acs.joc.5b02229. Epub 2015 Dec 1.
Studies of antidiabetic vanadium compounds, specifically the organic vanadate esters, are reviewed with regard to their chemistry and biological properties. The compounds are described from the perspective of how the fundamental chemistry and properties of organic vanadate esters impact their effect
PMID 26544762

Synthesis and structural characterization of AMV2O8 (A = K, Rb, Tl, Cs; M = Nb, Ta) vanadates: a structural comparison of A(+)M(5+)V2O8 vanadates and A(+)M(5+)P2O8 phosphates.

Paidi AK1, Devi RN, Vidyasagar K.
Dalton transactions (Cambridge, England : 2003).Dalton Trans.2015 Oct 21;44(39):17399-408. doi: 10.1039/c5dt02618k. Epub 2015 Sep 21.
Eight new quaternary vanadates of niobium and tantalum, AMV2O8 (A = K, Rb, Tl, Cs; M = Nb, Ta), have been prepared by solid state reactions and structurally characterized by single crystal and powder X-ray diffraction (XRD) techniques. The two cesium compounds, unlike the known CsSbV2O8 with a layer
PMID 26390384

Japanese Journal

Synthesis and Characterization of a Palladium-supported Fluoride-incorporated Dodecavanadate

Khair Miftahul,Kikukawa Yuji,Hayashi Yoshihito
Chemistry Letters 46(9), 1406-1408, 2017
… By the oxidation of decavanadate {n-Bu4N}4[V10O26] in the presence of F− …
NAID 130006067877

A highly-flexible cyclic-decavanadate ligand for interconversion of dinuclear- and trinuclear-cobalt(II) and manganese(II) cores

Maruyama Tatsuya,Kikukawa Yuji,Sakiyama Hiroshi,Katayama Misaki,Inada Yasuhiro,Hayashi Yoshihito
RSC Advances 7(60), 37666-37674, 2017
… Cyclic decavanadate ligands exhibit versatility in the number and the direction of the coordination sites by changing the conformation to stabilize various multinuclear-metal-cores, while organic multinucleating ligands require specific design for each of the multimetal complexes due to their structure directing ability. … The flexibility of cyclic decavanadate ligands is demonstrated here to achieve accommodation of dinuclear or trinuclear units by using the same ligand. …
NAID 120006374151

Synthesis and characterization of fluoride-incorporated polyoxovanadates

Kikukawa Yuji,Yokoyama Taiga,Kashio Sanae,Hayashi Yoshihito
Journal of Inorganic Biochemistry (147), 221-226, 2015-06-01
… The structural gap between tetrahedral-unit-based metavanadate and octahedral-unit-based decavanadate structures may be linked by this hybrid complex. …
NAID 120005649580

Related Pictures

โยชิฮิโตะ ฮายาชิ - มหาวิทยาลัย [Frontiers in Bioscience 9, 1759-1770, May 1, 2004] A Comparison between Vanadyl, Vanadate, and Decavanadate Effects in Actin Structure Sensitivity of the microfabricated NMR insert. 1H spectrum at 700 MHz | Download Recent perspectives into biochemistry of decavanadate Polyoxometalate - Wikipedia Aligarh Muslim University || Department Page (IUCr) Dipotassium bis[hexaaquacobalt(II)] decavanadate tetrahydrate

★リンクテーブル★

リンク元	「orthovanadate」「vanadate」「デカバナジン酸」「sodium vanadate」「metavanadate」

「orthovanadate」

Sodium decavanadate
Identifiers
CAS Number	12315-57-0 ;
Properties
Chemical formula	Na6[V10O28]
Molar mass	1419.6 g
Appearance	orange solid
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	(what is ?)
	Infobox references

　　[★]

バナジン酸、(化合物)バナジン酸塩、正バナジン酸塩

関: decavanadate、metavanadate、sodium vanadate、vanadate、vanadic acid、vanadyl

「vanadate」

　　[★]

バナジン酸、バナジン酸塩

関: decavanadate、metavanadate、orthovanadate、sodium vanadate、vanadic acid、vanadyl

「デカバナジン酸」

　　[★]

英: decavanadate
関: バナジン酸塩、メタバナジン酸、バナジン酸ナトリウム、バナジル

「sodium vanadate」

　　[★]

バナジン酸ナトリウム

関: decavanadate、metavanadate、orthovanadate、vanadate、vanadyl

「metavanadate」

　　[★]

メタバナジン酸

関: decavanadate、orthovanadate、sodium vanadate、vanadate、vanadyl

[one-1] ^ ^a ^b ^c ^d ^e ^f ^g Johnson, G.; Murmann, R. K. (2007). Sodium and Ammonium Decavanadates. Inorganic Syntheses. 19. pp. 140–145. doi:10.1002/9780470132500.ch32.CS1 maint: uses authors parameter (link)

[two-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.CS1 maint: uses authors parameter (link)

[three-3] ^ ^a ^b ^c ^d ^e ^f ^g ^h Evans Jr., H. T. (1966). "The molecular structure of the isopoly complex ion, decavanadate". Inorg. Chem. 5: 967–977. doi:10.1021/ic50040a004.CS1 maint: uses authors parameter (link)

[four-4] 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.CS1 maint: uses authors parameter (link)

[five-5] Rehder, D. (2008). Bioinorganic Vanadium Chemistry. Wiley & Sons. pp. 13–51. ISBN 978-0-470-06509-9.CS1 maint: uses authors parameter (link)

[six-6] Durif, P.A.; Averbuch-pouchot, M.T. (1980). "Structure d'un Décavanadate d'Hexasodium Hydraté". Acta Crystallogr. B. 36 (3): 680–682. doi:10.1107/S0567740880004116.CS1 maint: uses authors parameter (link)

[seven-7] Tracey, A.S.; Crans, D.C. (1998). Vanadium Compounds. Washington D.C.: American Chemical Society. ISBN 0-8412-3589-9.

[eight-8] Day, 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.CS1 maint: uses authors parameter (link)

[nine-9] 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.CS1 maint: uses authors parameter (link)

[ten-10] Matias, P.M.; Pessoa, J.C.; Duarte, M.T.; Maderia, C. (2000). "Tetrapotassium disodium decavanadate(V) decahydrate". Acta Crystallogr. C. 57 (3): e75–e76. doi:10.1107/S0108270100001530. PMID 15263200.CS1 maint: uses authors parameter (link)

[eleven-11] Escobar, M.E.; Baran, E.J. (1981). "Die Schwingungsspektren einiger kristalliner Dekavanadate". Monatshefte für Chemie. 112: 43–49. doi:10.1007/BF00906241.CS1 maint: uses authors parameter (link)

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案内

decavanadate