Osmium(IV) Chloride - Preparation, Structure, Reactions

Preparation, Structure, Reactions

It was first reported in 1909 as the product of chlorination of osmium metal. This route affords the high temperature polymorph:

Os + 2 Cl2 → OsCl4

This reddish-black polymorph is orthorhombic and adopts a structure in which osmium centres are octahedrally coordinated, sharing opposite edges of the OsCl6 octahedra to form a chain. A brown, apparently cubic polymorph forms upon reduction of osmium tetroxide with thionyl chloride:

OsO4 + 4 SOCl2 → OsCl4 + 2 Cl2 + 4 SO2

Osmium tetraoxide dissolves in hydrochloric acid to give the hexachloroosmate anion:

OsO4 + 8 HCl → H2OsCl6 + Cl2 + 4 H2O

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