Potassium octachlorodimolybdate

Potassium octachlorodimolybdate(4−)
Identifiers
3D model (JSmol)
  • InChI=1S/8ClH.4K.2Mo/h8*1H;;;;;;/q;;;;;;;;4*+1;2*+2/p-8
    Key: IPKVUDXOBCRDJX-UHFFFAOYSA-F
  • [K+].[K+].[K+].[K+].Cl[Mo-2](Cl)(Cl)(Cl)$[Mo-2](Cl)(Cl)(Cl)Cl
Properties
K4[Mo2Cl8]
Molar mass 631.89 g·mol−1
Appearance red crystals
Density 2.54 g/cm3
soluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Potassium octachlorodimolybdate (systematically named potassium bis(tetrachloromolybdate)(Mo–Mo)(4−)) is an inorganic compound with the chemical formula K4[Mo2Cl8]. 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.

The octachlorodimolybdate(II) anion, [Mo2Cl8]4−, which features a quadruple Mo–Mo bond

The compound is prepared in two steps from molybdenum hexacarbonyl:[1][2]

2 Mo(CO)6 + 4 CH3CO2H → (CH3CO2)4Mo2 + 2 H2 + 12 CO
(CH3CO2)4Mo2 + 4 HCl + 4 KCl → K4[Mo2Cl8] + 4 CH3CO2H

The reaction of the acetate with HCl was first described as providing trimolybdenum compounds,[3] but subsequent crystallographic analysis confirmed that the salt contains the [Cl4Mo≣MoCl4]4− anion, with D4h symmetry, in which the two Mo atoms are linked by a quadruple bond. Each Mo atom is bounded with four Cl− ligands by a single bond. Each MoCl4 group is a regular square pyramid, with an Mo atom at the apex, and four Cl atoms at the vertices of the square base of the pyramid. The Mo–Mo distance is 214 pm.[4]

References

  1. ^ Brignole, A. B.; Cotton, F. A.; Dori, Z. (1972). "Rhenium and Molybdenum Compounds Containing Quadruple Bonds". Inorganic Syntheses. Vol. 13. pp. 81–89. doi:10.1002/9780470132449.ch15. ISBN 978-0-470-13244-9. {{cite book}}: |journal= ignored (help)
  2. ^ Girolami, G. S.; Rauchfuss, T. B.; Angelici, R. J. (1999). Synthesis and Technique in Inorganic Chemistry. Mill Valley, CA: University Science Books. ISBN 978-0-935702-48-4.
  3. ^ Allison, G. B.; Anderson, I. R.; Sheldon, J. C. (1967). "The Preparation of Halogenotrimolybdate(II) Compounds". Aust. J. Chem. 20 (5): 869–876. doi:10.1071/CH9670869.
  4. ^ Brencic, Jurij V.; Cotton, F. Albert (1969). "Octachlorodimolybdate(II) Ion. Species with a Quadruple Metal–Metal Bond". Inorg. Chem. 8: 7–10. doi:10.1021/ic50071a002.