Sodium hexachloroosmate

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Sodium hexachloroosmate
Na2OsCl6.svg
Two-dimensional representation of disodium hexachloroosmate salt
Na2OsCl6(aq).jpg
A solution of sodium hexachloroosmate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.775 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • monohydrate:InChI=1S/6ClH.2Na.H2O.Os/h6*1H;;;1H2;/q;;;;;;2*+1;;+4/p-6
    Key: PQSWAUXOSHGRPF-UHFFFAOYSA-H
  • anhydrous:InChI=1S/6ClH.2Na.Os/h6*1H;;;/q;;;;;;2*+1;+4/p-6
    Key: PVTVRPSPEDISMV-UHFFFAOYSA-H
  • monohydrate:O.[Na+].[Na+].Cl[Os-2](Cl)(Cl)(Cl)(Cl)Cl
  • anhydrous:[Na+].[Na+].[Cl-].[Cl-].Cl[Os](Cl)(Cl)Cl
Properties
Cl6Na2Os
Molar mass 448.91 g·mol−1
Appearancered solid
Density 3.221 g/cm3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Sodium hexachloroosmate is the inorganic compound with the formula Na2OsCl6. A red solid, it is the disodium salt of the osmium(IV) complex [OsCl6]2−. The anion is an octahedral complex with Os-Cl distance of 2.325(3) Å, as established by X-ray crystallography. [1] The compound can be prepared by reaction of a suspension of osmium metal in molten sodium chloride with chlorine: [2]

Os + 2 NaCl + 2 Cl2 → Na2OsCl6

Hexachloroosmate is paramagnetic, with a low-spin d4 configuration.

Reactions

Sodium hexachloroosmate reacts with a solution of ammonium chloride to produce ammonium hexachloroosmate(IV). Upon exposure to strong alkali, hexachloroosmates will decompose to osmium dioxide. They react with excess ammonia to form so-called osmium diammine hydroxide, OsO(NH3)2(OH)2 [3] [4]

Sodium hexachloroosmate reacts with triphenylphosphine to form various complexes. When a solution of sodium hexachloroosmate and formalin is added to a boiling solution of triphenylphosphine in 2-methoxyethanol, OsHCl(CO)(PPh3)3 is formed. [5]

Na2OsCl6•6H2O + 3(C6H5)3Pformalin
———→OsHCl(CO)[P(C6H5)3]3

With an aqueous solution containing potassium hydroxide and formaldehyde they react to produce OsH2(CO)(PPh3)3. [5]

Na2OsCl6•6H2O + 3(C6H5)3Pkoh hcho
———→OsH2(CO)[P(C6H5)3]3

With ethanol and sodium borohydride they react to produce OsH4[P(C6H5)3]3. [5]

Na2OsCl6•6H2O + 3(C6H5)3Pborohydride
————→OsH4[P(C6H5)3]3

With 2-methoxyethanol and n-methyl-n-nitrosotoluene sulfonamide they react to yield OsCl3(NO)[P(C6H5)3]2. [5]

Na2OsCl6•6H2O + 2(C6H5)3P + p-TolSO2N(NO)(CH3) → OsCl3(NO)[P(C6H5)3]2.

References

  1. ↑ Rudnitskaya, O. V.; Kultyshkina, E. K.; Dobrokhotova, E. V.; Tereshina, T. A.; Popova, A. S.; Zubavichus, Ya. V.; Khrustalev, V. N. (2019). "Crystal Structure of Na2[OsCl6]". Journal of Structural Chemistry. 60 (7): 1086–1090. doi:10.1134/S0022476619070096. S2CID   199474647.
  2. ↑ H. L. Grube (1963). "Sodium Hexachloroosmate(VI)". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 2pages=1602. NY, NY: Academic Press.
  3. ↑ Prakash Satya (2013). "Platinum Metals-IV:Osmium". Advanced Chemistry of Rare Elements, 5th Ed. India: S Chand and Company Limited. p. 710.
  4. ↑ J. Newton Friend (1920). "Osmium and its compounds". A textbook of inorganic chemistry, vol.IX Part I Cobalt, Nickel, and The Elements of The Platinum Group (PDF). London: Charles Griffin and Company, Limited. p. 216. Retrieved 18 July 2025.
  5. 1 2 3 4 Parshall, George (1974). Inorganic Syntheses (PDF). Vol. 15. McGraw-Hill Book Company. pp. 53–58. Retrieved 17 July 2025.
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