Synthesis, Structures and Properties of Double Complex Salts [M(Phen)3][RuNOCl5]·3H2O (M = Ni, Cu)

New double complex salts [Cu(Phen)3][RuNOCl5]·3H2O and [Ni(Phen)3][RuNOCl5]·3H2O have been synthesized and their crystal structures have been determined. The thermal properties of the synthesized DCS have been studied in inert and reducing atmospheres using synchronous TG–DTA/EGA–MS analysis and ex situ X-ray powder diffraction of the intermediate and final thermolysis products. The final thermolysis products of [Cu(Phen)3][RuNOCl5]·3H2O in inert and reducing atmospheres are a mixture of copper and ruthenium, while the thermal decomposition product of [Ni(Phen)3][RuNOCl5]·3H2O in an inert atmosphere is a mixture of nickel and ruthenium. Thermolysis of [Ni(Phen)3][RuNOCl5]·3H2O in a reducing atmosphere up to 400°C leads to the formation of metastable solid solutions NixRuz–x with a high content of components (x ≤ 0.24). An increase in the thermolysis temperature to 800°C leads to partial decomposition of the solid solution.