Study of nitrosation of hexaammineruthenium(II): Crystal structure of trans-[RuNO(NH3)(4)Cl]Cl-2

The nitrosation of [Ru(NH3)(6)](2+) in hydrochloric acid and alkaline ammonia media has been studied; the patterns of interconversion of ruthenium complexes in reaction solutions have been proposed. In both cases, nitrogen(II) oxide acts as the nitrosation agent. The procedure for the synthesis of [Ru(NO)(NH3)(5)]Cl-3 center dot H2O (yield 75-80%), the main nitrosation product of [Ru(NH3)(6)](2+), has been optimized. Thermolysis of [Ru(NO)(NH3)(5)]Cl-3 center dot H2O in a helium atmosphere has been studied; the intermediates have been identified. One of these products is polyamidodichloronitrosoruthenium(II) whose subsequent decomposition gives an equimolar mixture of ruthenium metal and dioxide. The structure of trans-[RuNO(NH3)(4)Cl]Cl-2, formed in the second stage of thermolysis and as a by-product in the nitrosation of [Ru(NH3)(6)]Cl-2, has been determined by X-ray diffraction.