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:[K+].[K+].[K+].[K+].N#C[Mo-4](C#N)(C#N)(C#N)(C#N)(C#N)(C#N)C#N
  • dihydrate:O.O.[K+].[K+].[K+].[K+].N#C[Mo-4](C#N)(C#N)(C#N)(C#N)(C#N)(C#N)C#N
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]

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3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
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O2−
7
, Cr
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O2−
10
and Cr
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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). "Cyanide Compounds". Inorganic Syntheses. Vol. 34. p. 156. doi:10.1002/0471653683.ch4. ISBN   978-0-471-64750-8.
  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