Potassium octacyanomolybdate(IV)

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Potassium octacyanomolybdate(IV)
K4Mo(CN)8 chemdraw.png
K4Mo(CN)8 avogadro1.png
Names
IUPAC name
Potassium octacyanidomolybdate(IV)
Other names
Potassium octacyanomolybdate(IV)
Identifiers
3D model (JSmol)
PubChem CID
  • dihydrate:InChI=1S/8CN.4K.Mo.H2O/c8*1-2;;;;;;/h;;;;;;;;;;;;;1H2/q8*-1;4*+1;+4;
    Key: JJVZTQPHXSHIOV-UHFFFAOYSA-N
  • anhydrous:O.[K+].[K+].[K+].[K+].N#C[Mo-4](C#N)(C#N)(C#N)(C#N)(C#N)(C#N)C#N
  • dihydrate:[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.O.[K+].[K+].[K+].[K+].[Mo+4]
Properties
K4[Mo(CN)8]
Molar mass 460,47 g/mol (anhydrous)
496.5 g/mol (dihydrate)
Appearanceyellow powder
Melting point >300 °C
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H302, H315, H319, H335
P261, P305+P351+P338
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Potassium octacyanomolybdate(IV) is the inorganic salt with the formula K4[Mo(CN)8]. A yellow light-sensitive solid, it is the potassium salt of the cyanometalate with the coordination number eight. The complex anion consists of a Mo(IV) center bound to eight cyanide ligands resulting in an overall charge of −4, which is balanced with four potassium cations. The salt is often prepared as its dihydrate K4[Mo(CN)8].(H2O)2.

Contents

Preparation

The dihydrate K4[Mo(CN)8] · 2 H2O can be prepared by the reduction of molybdate (MoO42-) with potassium borohydride (KBH4) in a solution with potassium cyanide and acetic acid. [1] [2] Yields of 70% are typical and the method is suited for scale-up.

4 MoO42- + 32 CN + BH4 + 25 H+ → 4  [Mo(CN)8]4- + 13 H2O + H3BO3

An alternative route starts from MoCl4(Et2O)2 avoiding the need for reductants. The yield of this route is typically around 70%. [3] This synthesis is convenient for lower batch sizes than the earlier method but the MoCl4(Et2O)2 is typically less available than the molybdate.

MoCl4(Et2O)2 + 8 KCN → K4[Mo(CN)8] + 4 KCl + 2 Et2O

Reactions

Octacyanomolybdate(IV) can be oxidized to the paramagnetic octacyanomolybdate(V).

The cyanide ligands in [Mo(CN)8]4- remain basic. Strong acids lead to the hydrogen isocyanide complex [Mo(CNH)8]4+, in common with many cyanometalate complexes. [4] These ligands can be substituted by others, for example H2O. The cyanide ligands also bind to other metals, leading to cages. [2]

Related Research Articles

Potassium ferrocyanide Chemical compound

Potassium ferrocyanide is the inorganic compound with formula K4[Fe(CN)6]·3H2O. It is the potassium salt of the coordination complex [Fe(CN)6]4−. This salt forms lemon-yellow monoclinic crystals.

Cuprate loosely refers to a material that can be viewed as containing anionic copper complexes. Examples include tetrachloridocuprate ([CuCl4]2−), the superconductor YBa2Cu3O7, and the organocuprates (e.g., dimethylcuprate [Cu(CH3)2]). The term cuprates derives from the Latin word for copper, cuprum. The term is mainly used in three contexts: oxide materials, anionic coordination complexes, and anionic organocopper compounds.

Manganese(II) chloride Chemical compound

Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations. It is a paramagnetic salt.

Cobalt(II) chloride Chemical compound

Cobalt(II) chloride is an inorganic compound of cobalt and chlorine, with the formula CoCl
2
. The compound forms several hydrates CoCl
2
nH
2
O
, for n = 1, 2, 6, and 9. Claims of the formation of tri- and tetrahydrates have not been confirmed. The anhydrous form is a blue crystalline solid; the dihydrate is purple and the hexahydrate is pink. Commercial samples are usually the hexahydrate, which is one of the most commonly used cobalt compounds in the lab.

Cyanate

Cyanate is an anion with the structural formula [O=C=N], usually written OCN. It also refers to any salt containing it, such as ammonium cyanate.

Molybdenum trioxide is chemical compound with the formula MoO3. This compound is produced on the largest scale of any molybdenum compound. It is an intermediate in the production of molybdenum metal. It is also an important industrial catalyst. Molybdenum trioxide occurs as the rare mineral molybdite.

Quadruple bond Chemical bond involving eight electrons; has one sigma, two pi, and one delta bond

A quadruple bond is a type of chemical bond between two atoms involving eight electrons. This bond is an extension of the more familiar types double bonds and triple bonds. Stable quadruple bonds are most common among the transition metals in the middle of the d-block, such as rhenium, tungsten, technetium, molybdenum and chromium. Typically the ligands that support quadruple bonds are π-donors, not π-acceptors.

Borohydride

Borohydride refers to the anion [BH4], which is also called tetrahydroborate, and its salts. Borohydride or hydroborate is also the term used for compounds containing [BH4-nXn], where n is an integer from 0 to 3, for example cyanoborohydride or cyanotrihydroborate [BH3(CN)] and triethylborohydride or triethylhydroborate [BH(CH2CH3)3]. Borohydrides find wide use as reducing agents in organic synthesis. The most important borohydrides are lithium borohydride and sodium borohydride, but other salts are well known. Tetrahydroborates are also of academic and industrial interest in inorganic chemistry.

Ammonium heptamolybdate Chemical compound

Ammonium heptamolybdate is the inorganic compound whose chemical formula is (NH4)6Mo7O24, normally encountered as the tetrahydrate. A dihydrate is also known. It is a colorless solid, often referred to as ammonium paramolybdate or simply as ammonium molybdate, although "ammonium molybdate" can also refer to ammonium orthomolybdate, (NH4)2MoO4, and several other compounds. It is one of the more common molybdenum compounds.

Potassium octachlorodimolybdate Chemical compound

Potassium octachlorodimolybdate is an inorganic compound with the chemical formula K4Mo2Cl8. It is known as a red-coloured, microcrystalline solid. The anion is of historic interest as one of the earliest illustrations of a quadruple bonding. The salt is usually obtained as the pink-coloured dihydrate.

Cobalt(II) cyanide is the inorganic compound with the formula Co(CN)2. It is coordination polymer that has attracted intermittent attention over many years in the area of inorganic synthesis and homogeneous catalysis.

Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

Cyanometallates or cyanometalates are a class of coordination compounds, most often consisting only of cyanide ligands. Most are anions. Cyanide is a highly basic and small ligand, hence it readily saturates the coordination sphere of metal ions. The resulting cyanometallate anions are often used as ligands for building more complex structures called coordination polymers, the best known example of which is Prussian blue, a common dyestuff.

Molybdate

In chemistry a molybdate is a compound containing an oxoanion with molybdenum in its highest oxidation state of 6. Molybdenum can form a very large range of such oxoanions which can be discrete structures or polymeric extended structures, although the latter are only found in the solid state. The larger oxoanions 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 oxoanions 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
2
O2−
7
, Cr
3
O2−
10
and Cr
4
O2−
13
ions which are all based on tetrahedral chromium. Tungsten is similar to molybdenum and forms many tungstates containing 6 coordinate tungsten.

Potassium octachlorodirhenate(III) is an inorganic compound with the formula K2Re2Cl8. This dark blue salt is well known as an early example of a compound featuring quadruple bond between its metal centers. Although the compound has no practical value, its characterization was significant in opening a new field of research into complexes with quadruple bonds.

Transition metal nitrile complexes Class of coordination compounds containing nitrile ligands (coordinating via N)

Transition metal nitrile complexes are coordination compounds containing nitrile ligands. Because nitriles are weakly basic, the nitrile ligands in these complexes are often labile.

Potassium dicyanoaurate is an inorganic compound with formula K[Au(CN)2]. It is a colorless to white solid that is soluble in water and slightly soluble in alcohol. The salt itself is often not isolated, but solutions of the dicyanoaurate ion ([Au(CN)2]) are generated on a large scale in the extraction of gold from its ores.

Transition metal chloride complex Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

Potassium tetracyanonickelate Chemical compound

Potassium tetracyanonickelate is the inorganic compound with the formula K2Ni(CN)4. It is usually encountered as the monohydrate but the anhydous salt is also known. Both are yellow, water-soluble, diamagnetic solids. The salt consists of potassium ions and the tetracyanonickelate coordination complex, which is square planar.

Potassium diplatinum(II) tetrakispyrophosphite Chemical compound

Potassium diplatinum(II) tetrakispyrophosphite (abbreviated as [Pt2(pop)4]4−) is the inorganic compound with the formula K4[Pt2(HO2POPO2H)4]. It is a water-soluble yellow salt. The compound has a long-lived, strongly luminescent excited state, with an emission maximum at ∼510 nm and a lifetime near 10 μs.

References

  1. Leipoldt, J. G.; Bok, L. D. C.; Cilliers, P. J. (1974). "The Preparation of Potassium Octacyanomolybdate(IV) Dihydrate". Zeitschrift für anorganische und allgemeine Chemie. 409 (3): 343–344. doi:10.1002/zaac.19744090310.
  2. 1 2 Bonadio, Federica; Larionova, Joulia; Gross, Mathias; Biner, Margret; Stoeckli‐Evans, Helen; Decurtins, Silvio; Pilkington, Melanie (2004). Cyano-Bridgeed M(II)9M(V)6 Molecular Clusters, M(II) = Mn, Co, Ni; M(V) = Mo, W. Inorganic Syntheses. Vol. 34. p. 156. doi:10.1002/0471653683.ch4.
  3. G. Handzlik, M. Magott, B. Sielucka, D. Pinkowicz, "Alternative Synthetic Route to Potassium Octacyanidoniobate(IV) and its Molybdenum Congener", Eur. J. Inorg. Chem., 2016, pp. 4872-77.doi : 10.1002/ejic.201600669
  4. M. Sellin, V. Marvaud, M. Malischewski, "Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from Superacids", Angew. Chem. Int. Ed., 2020 volume 59, pp. 10519-10522.doi : 10.1002/anie.202002366