Potassium osmate

Potassium osmate is the inorganic compound with the formula K2[OsO2(OH)4]. This diamagnetic purple salt contains osmium in the VI (6+) oxidation state.[1] When dissolved in water a pink solution is formed but when dissolved in methanol, the salt gives a blue solution.[1] The salt gained attention as a catalyst for the asymmetric dihydroxylation of olefins.[2]

Potassium osmate
Names
Other names
Potassium osmate(VI) dihydrate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.157.189
EC Number
  • 243-247-1
UNII
  • InChI=1S/2K.4H2O.2O.Os/h;;4*1H2;;;/q2*+1;;;;;2*-1;+4/p-4
    Key: DDTIHYGDUUGVNU-UHFFFAOYSA-J
  • [K+].[K+].[O-][Os](O)(O)(O)(O)[O-]
Properties
H4K2O6Os
Molar mass 368.42
Appearance purple solid
Hazards
GHS labelling:
GHS06: Toxic
Danger
H301, H311, H330, H331
P260, P261, P264, P270, P271, P280, P284, P301+P310, P302+P352, P304+P340, P310, P311, P312, P320, P321, P322, P330, P361, P363, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Structure

The complex anion is octahedral. Like related d2 dioxo complexes, the oxo ligands are trans.[3] The Os=O and Os-OH distances are 1.75(2) and 1.99(2) Å, respectively. It is a relatively rare example of a metal oxo complex that obeys the 18e rule.

Preparation

The compound was first reported by Edmond Frémy in 1844.[4] Potassium osmate is prepared by reducing osmium tetroxide with ethanol:[5]

2 OsO4 + C2H5OH + 5 KOH → CH3CO2K + 2 K2[OsO2(OH)4]

Alkaline oxidative fusion of osmium metal also affords this salt.[1]

See also

References

  1. F. Albert Cotton; Geoffrey Wilkinson (1966). Advanced Inorganic Chemistry: A Comprehensive Treatise. New York, Interscience Publishers. p. 1007.
  2. Li, Guigen; Chang, Han-Ting; Sharpless, K. Barry (1996). "Catalytic Asymmetric Aminohydroxylation (AA) of Olefins". Angew. Chem. Int. Ed. Engl. 35 (4): 451–4. doi:10.1002/anie.199604511.
  3. R. K. Murmann, C. L. Barnes "Redetermination of the crystal structure of potassium trans-(dioxo)-tetra(hydroxo)osmate(VI), K2[Os(OH)4(O)2]" Z. Kristallogr. NCS 217, 2002, pp. 303–304. doi:10.1524/ncrs.2002.217.jg.303
  4. Frémy, E. "Ueber das Osmium" Journal für Praktische Chemie 1844 vol.33, 406-416. doi:10.1002/prac.18440330160
  5. John M. Malin (1980). "Potassium Tetrahydroxodioxoosmate(VI) and trans ‐Bis(Ethylenediamine)Dioxoosmium(VI) Chloride". Potassium Tetrahydroxodioxoosmate(VI) and trans-Bis(Ethylenediamine)Dioxoosmium(VI) Chloride. Inorganic Syntheses. Vol. 20. pp. 61–63. doi:10.1002/9780470132517.ch18. ISBN 9780470132517.
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