Vanadate

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Orthovanadate anion.svg

In chemistry, a vanadate is an anionic coordination complex of vanadium. Often vanadate refers to oxoanions of vanadium, most of which exist in its highest oxidation state of +5. The complexes [V(CN)6]3− and [V2Cl9]3− are referred to as hexacyanovanadate(III) and nonachlorodivanadate(III), respectively.

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A simple vanadate ion is the tetrahedral orthovanadate anion, VO3−4 (which is also called vanadate(V)), which is present in e.g. sodium orthovanadate and in solutions of V2O5 in strong base (pH  > 13 [1] ). Conventionally this ion is represented with a single double bond, however this is a resonance form as the ion is a regular tetrahedron with four equivalent oxygen atoms.

Additionally a range of polyoxovanadate ions exist which include discrete ions and "infinite" polymeric ions. [2] There are also vanadates, such as rhodium vanadate, RhVO4, which has a statistical rutile structure where the Rh3+ and V5+ ions randomly occupy the Ti4+ positions in the rutile lattice, [3] that do not contain a lattice of cations and balancing vanadate anions but are mixed oxides.

In chemical nomenclature when vanadate forms part of the name, it indicates that the compound contains an anion with a central vanadium atom, e.g. ammonium hexafluorovanadate is a common name for the compound [NH4]3[VF6] with the IUPAC name of ammonium hexafluoridovanadate(III).

Examples of oxovanadate ions

Some examples of discrete ions are

Some examples of polymeric "infinite" ions are

Ammonium-metavanadate-chains-3D.png
V5O14 ball and stick.png
Decavanadate polyhedra.png
metavanadate chains
V5O14
decavanadate ion

In these ions vanadium exhibits tetrahedral, square pyramidal and octahedral coordination. In this respect vanadium shows similarities to tungstate and molybdate, whereas chromium however has a more limited range of ions.

Aqueous solutions

Dissolution of vanadium pentoxide in strongly basic aqueous solution gives the colourless VO3−4 ion. On acidification, this solution's colour gradually darkens through orange to red at around pH 7. Brown hydrated V2O5 precipitates around pH 2, redissolving to form a light yellow solution containing the [VO2(H2O)4]+ ion. The number and identity of the oxyanions that exist between pH 13 and 2 depend on pH as well as concentration. For example, protonation of vanadate initiates a series of condensations to produce polyoxovanadate ions: [2]

Pharmacological properties

Vanadate is a potent inhibitor of certain plasma membrane ATPases, such as Na+/K+-ATPase and Ca2+-ATPase (PMCA). Acting as a transition-state analog of phosphate, vanadate undergoes nucleophillic attack by water during phosphoryl transfer, essentially "trapping" P-type ATPases in their phosphorylated E2 state. [11] [12] It also inhibits skeletal muscle actomyosin MgATPase activity [13] and calcium activated force generation by actomyosin in the intact skeletal muscle contractile apparatus. [14] However, it does not inhibit other ATPases, such as SERCA (sarco/endoplasmic reticulum Ca2+-ATPase) or mitochondrial ATPase. [15] [16] [17]

Related Research Articles

<span class="mw-page-title-main">Vanadium</span> Chemical element, symbol V and atomic number 23

Vanadium is a chemical element; it has symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer (passivation) somewhat stabilizes the free metal against further oxidation.

<span class="mw-page-title-main">Vanadinite</span> Apatite supergroup, vanadate mineral

Vanadinite is a mineral belonging to the apatite group of phosphates, with the chemical formula Pb5(VO4)3Cl. It is one of the main industrial ores of the metal vanadium and a minor source of lead. A dense, brittle mineral, it is usually found in the form of red hexagonal crystals. It is an uncommon mineral, formed by the oxidation of lead ore deposits such as galena. First discovered in 1801 in Mexico, vanadinite deposits have since been unearthed in South America, Europe, Africa, and North America.

An oxyanion, or oxoanion, is an ion with the generic formula A
xOz−
y. Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determined by the octet rule. The corresponding oxyacid of an oxyanion is the compound H
zA
xO
y. The structures of condensed oxyanions can be rationalized in terms of AOn polyhedral units with sharing of corners or edges between polyhedra. The oxyanions adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) are important in biology.

<span class="mw-page-title-main">Group 5 element</span> Group of elements in the periodic table

Group 5 is a group of elements in the periodic table. Group 5 contains vanadium (V), niobium (Nb), tantalum (Ta) and dubnium (Db). This group lies in the d-block of the periodic table. This group is sometimes called the vanadium group or vanadium family after its lightest member; however, the group itself has not acquired a trivial name because it belongs to the broader grouping of the transition metals.

<span class="mw-page-title-main">Polyoxometalate</span> Ion with many transition metals

In chemistry, a polyoxometalate is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed 3-dimensional frameworks. The metal atoms are usually group 6 or less commonly group 5 and group 7 transition metals in their high oxidation states. Polyoxometalates are often colorless, orange or red diamagnetic anions. Two broad families are recognized, isopolymetalates, composed of only one kind of metal and oxide, and heteropolymetalates, composed of one or more metals, oxide, and eventually a main group oxyanion. Many exceptions to these general statements exist.

<span class="mw-page-title-main">Vanadium(V) oxide</span> Precursor to vanadium alloys and industrial catalyst

Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V2O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.

<span class="mw-page-title-main">Tellurate</span> Compound containing an oxyanion of tellurium

In chemistry tellurate is a compound containing an oxyanion of tellurium where tellurium has an oxidation number of +6. In the naming of inorganic compounds it is a suffix that indicates a polyatomic anion with a central tellurium atom.

<span class="mw-page-title-main">Sodium oxalate</span> Chemical compound

Sodium oxalate, or disodium oxalate, is a chemical compound with the chemical formula Na2C2O4. It is the sodium salt of oxalic acid. It contains sodium cations Na+ and oxalate anions C2O2−4. It is a white, crystalline, odorless solid, that decomposes above 290 °C.

<span class="mw-page-title-main">Heteropolymetalate</span> Ion with many transition metals

In chemistry, the heteropolymetalates are a subset of the polyoxometalates, which consist of three or more transition metal oxyanions linked together by shared oxygen atoms to form a closed 3-dimensional molecular framework. In contrast to isopolymetalates, which contain only one kind of metal atom, the heteropolymetalates contain differing main group oxyanions. The metal atoms are usually group 6 or less commonly group 5 transition metals in their highest oxidation states. They are usually colorless to orange, diamagnetic anions. For most heteropolymetalates the W, Mo, or V, is complemented by main group oxyanions phosphate and silicate. Many exceptions to these general statements exist, and the class of compounds includes hundreds of examples.

<span class="mw-page-title-main">Sodium orthovanadate</span> Chemical compound

Sodium orthovanadate is the inorganic compound with the chemical formula Na3V O4. It forms a dihydrate Na3VO4·2H2O. Sodium orthovanadate is a salt of the VO3−4 oxyanion. It is a colorless, water-soluble solid.

<span class="mw-page-title-main">Tetrahedral molecular geometry</span> Central atom with four substituents located at the corners of a tetrahedron

In a tetrahedral molecular geometry, a central atom is located at the center with four substituents that are located at the corners of a tetrahedron. The bond angles are cos−1(−1⁄3) = 109.4712206...° ≈ 109.5° when all four substituents are the same, as in methane as well as its heavier analogues. Methane and other perfectly symmetrical tetrahedral molecules belong to point group Td, but most tetrahedral molecules have lower symmetry. Tetrahedral molecules can be chiral.

<span class="mw-page-title-main">Ammonium metavanadate</span> Chemical compound

Ammonium metavanadate is the inorganic compound with the formula NH4VO3. It is a white salt, although samples are often yellow owing to impurities of V2O5. It is an important intermediate in the purification of vanadium.

In chemistry, hypomanganate, also called manganate(V) or tetraoxidomanganate(3−), is a trivalent anion (negative ion) composed of manganese and oxygen, with formula MnO3−
4.

<span class="mw-page-title-main">Vanadium compounds</span>

Vanadium compounds are compounds formed by the element vanadium (V). The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5, whereas the chemistry of the other group 5 elements, niobium and tantalum, are somewhat more limited to the +5 oxidation state. In aqueous solution, vanadium forms metal aquo complexes of which the colours are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives, which contain the VO2+ center.

<span class="mw-page-title-main">Vanadyl ion</span>

The vanadyl or oxovanadium(IV) cation, VO2+, is a functional group that is common in the coordination chemistry of vanadium. Complexes containing this functional group are characteristically blue and paramagnetic. A triple bond is proposed to exist between the V4+ and O2− centers. The description of the bonding in the vanadyl ion was central to the development of modern ligand-field theory.

Thiophosphates (or phosphorothioates, PS) are chemical compounds and anions with the general chemical formula PS
4−xO3−
x (x = 0, 1, 2, or 3) and related derivatives where organic groups are attached to one or more O or S. Thiophosphates feature tetrahedral phosphorus(V) centers.

A stannide can refer to an intermetallic compound containing tin combined with one or more other metals; an anion consisting solely of tin atoms or a compound containing such an anion, or, in the field of organometallic chemistry an ionic compound containing an organotin anion

<span class="mw-page-title-main">Amavadin</span> Chemical compound

Amavadin is a vanadium-containing anion found in three species of poisonous Amanita mushrooms: A. muscaria, A. regalis, and A. velatipes. Amavadin was first isolated and identified in 1972 by Kneifel and Bayer. This anion, which appears as a blue solution, is an eight-coordinate vanadium complex. A Ca2+ cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction. Oxidized amavadin can be isolated as its PPh4+ salt. The oxidized form contains vanadium(V), which can be used to obtain an NMR spectrum.

<span class="mw-page-title-main">Molybdate</span> Chemical compound of the form –O–MoO₂–O–

In chemistry, a molybdate is a compound containing an oxyanion with molybdenum in its highest oxidation state of 6: O−−Mo(=O)2−O−. Molybdenum can form a very large range of such oxyanions, which can be discrete structures or polymeric extended structures, although the latter are only found in the solid state. The larger oxyanions are members of group of compounds termed polyoxometalates, and because they contain only one type of metal atom are often called isopolymetalates. The discrete molybdenum oxyanions range in size from the simplest MoO2−
4, found in potassium molybdate up to extremely large structures found in isopoly-molybdenum blues that contain for example 154 Mo atoms. The behaviour of molybdenum is different from the other elements in group 6. Chromium only forms the chromates, CrO2−
4, Cr
2O2−
7, Cr
3O2−
10 and Cr
4O2−
13 ions which are all based on tetrahedral chromium. Tungsten is similar to molybdenum and forms many tungstates containing 6 coordinate tungsten.

<span class="mw-page-title-main">Sodium decavanadate</span> Chemical compound

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−. Numerous other decavanadate salts have been isolated and studied since 1956 when it was first characterized.

References

  1. ↑ Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN   0-471-19957-5
  2. 1 2 3 4 5 6 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  3. ↑ Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN   0-19-855370-6
  4. ↑ Hamilton E. E.; Fanwick P.E.; Wilker J.J. (2002). "The Elusive Vanadate (V3O9)3−: Isolation, Crystal Structure, and Nonaqueous Solution Behavior". J. Am. Chem. Soc. 124 (1): 78–82. doi:10.1021/ja010820r. PMID   11772064.
  5. ↑ G.-Y. Yang, D.-W. Gao, Y. Chen, J.-Q. Xu, Q.-X. Zeng, H.-R. Sun, Z.-W. Pei, Q. Su, Y. Xing, Y.-H. Ling and H.-Q. Jia (1998). "[Ni(C10H8N2)3]2[V4O12]·11H2O". Acta Crystallographica C. 54 (5): 616–618. Bibcode:1998AcCrC..54..616Y. doi:10.1107/S0108270197018751.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  6. ↑ V. W. Day; Walter G. Klemperer; O. M. Yaghi (1989). "A new structure type in polyoxoanion chemistry: synthesis and structure of the V
    5    O3−
    14     anion". J. Am. Chem. Soc. 111 (12): 4518. doi:10.1021/ja00194a068.
  7. ↑ Guang-Chuan Ou.; Long Jiang; Xiao-Long Feng; Tong-Bu Lu (2009). "Vanadium polyoxoanion-bridged macrocyclic metal complexes: from one-dimensional to three-dimensional structures". Dalton Transactions . 1 (1): 71–76. doi:10.1039/B810802A. PMID   19081973. S2CID   35209358.
  8. ↑ Hou D.; Hagen K.D.; Hill C.L. (1992). "Tridecavanadate, [V13O34]3−, a new high-potential isopolyvanadate". J. Am. Chem. Soc. 114 (14): 5864. doi:10.1021/ja00040a061.
  9. ↑ Müller A.; Sessoli R.; Krickemeyer E.; Bögge H.; Meyer J.; Gatteschi D.; Pardi L.; Westphal J.; Hovemeier K.; Rohlfing R.; Döring J; Hellweg F.; Beugholt C.; Schmidtmann M. (1997). "Polyoxovanadates: High-Nuclearity Spin Clusters with Interesting Host–Guest Systems and Different Electron Populations. Synthesis, Spin Organization, Magnetochemistry, and Spectroscopic Studies". Inorg. Chem. 36 (23): 5239. doi:10.1021/ic9703641.
  10. ↑ Jouanneau, S.; Verbaere, A.; Guyomard, D. (2003). "On a new calcium vanadate: synthesis, structure and Li insertion behaviour". Journal of Solid State Chemistry. 172 (1): 116–122. Bibcode:2003JSSCh.172..116J. doi:10.1016/S0022-4596(02)00164-0.
  11. ↑ Kühlbrandt, Werner (April 2004). "Biology, structure and mechanism of P-type ATPases". Nature Reviews. Molecular Cell Biology. 5 (4): 282–295. doi:10.1038/nrm1354. ISSN   1471-0072. PMID   15071553. S2CID   24927167.
  12. ↑ Davies, Douglas R.; Hol, Wim G.J. (2004-11-19). "The power of vanadate in crystallographic investigations of phosphoryl transfer enzymes". FEBS Letters. 577 (3): 315–321. doi: 10.1016/j.febslet.2004.10.022 . ISSN   0014-5793. PMID   15556602.
  13. ↑ Goodno, C.C.; Taylor, E.W. (1982). "Inhibition of actomyosin ATPase by vanadate". Proceedings of the National Academy of Sciences USA. 79 (1): 21–25. Bibcode:1982PNAS...79...21G. doi: 10.1073/pnas.79.1.21 . PMC   345653 . PMID   6459580.
  14. ↑ Wilson, G.J.; Shull, S.E.; Cooke, R. (1995). "Inhibition of muscle force by vanadate". Biophysical Journal. 68 (1): 216–226. Bibcode:1995BpJ....68..216W. doi: 10.1016/S0006-3495(95)80177-3 . PMC   1281679 . PMID   7711244.
  15. ↑ Luo D.; Nakazawa M.; Yoshida Y.; Cai J.; Imai S. (2000). "Effects of three different Ca2+ pump ATPase inhibitors on evoked contractions in rabbit aorta and activities of Ca2+ pump ATPases in porcine aorta". General Pharmacology: The Vascular System . 34 (3): 211–220. doi:10.1016/S0306-3623(00)00064-1. PMID   11120383.
  16. ↑ Bowman B.J.; Slayman C.W. (1979). "The Effects of Vanadate on the Plasma Membrane ATPase of Neurospora crassa". Journal of Biological Chemistry . 254 (8): 2928–2934. doi: 10.1016/S0021-9258(17)30163-1 . PMID   155060.
  17. ↑ Aureliano, Manuel; Crans, Debbie C. (2009). "Decavanadate (V
    10    O6−
    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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