Preparation and properties of some osmium nitrosylammines

Abstract

[Os(NH₃)₅I]I₂ and NO gave a mixture of [Os(NH₃)₅NO]I₃ and [OsI(NH₃)₄NO]I₂, which was converted to [Os(NH₃)₅NO] I₃ in liquid ammonia. [Os(NH₃)₅NO]X₃,H₂O (X = Cl, Br, or I) and OH^– gave [OsNH₂(NH₃)₄NO]X₂ reversibly, and under more vigorous conditions, trans-[OsOH(NH₃)₄NO]X₂. [OsOH(NH₃)₄NO]X₂, when refluxed with HX, gave [OsX(NH₃)₄NO]X₂. The physical properties of the complexes are reported and compared with the analogous ruthenium complexes. The complexes were unreactive to nucleophilic attack at the NO⁺ group, though [Os(NH₃)₅NO]³⁺ gave [Os(NH₃)₅N₂]²⁺ on refluxing with hydrazine.