Synthesis, structures, and thermolysis of new heterometallic cobalt, nickel, and copper complexes with the [Ru(NO)(NO2)4(OH)]2− anion as a ligand

Heterometallic complexes with pyridine-N-oxide (PyO), Ru(NO)(NO2)4(OH)Ni(PyO)2(H2O)] · CH3COCH3 (I), [{Ru(NO)(NO2)2(μ-NO2)2(μ-OH)Co}2(μ-PyO)] · H2O · CH3COCH (II), and [Ru(NO)(NO2)4(OH)Cu(PyO)2 (III), are isolated in the reactions of Na2[Ru(NO)(NO2)4(OH)] with nitrates of the corresponding metals in the presence of the organic ligand. The compounds synthesized are characterized by IR spectra, thermal analysis, and X-ray diffraction analysis. Depending on the M2+ cation, the ruthenium cation is coordinated through the bidentate (III, Cu2+) or tridentate (I, Ni2+ and II, CO2+) mode involving the bridging OH group and one or two NO2 groups. The thermal decomposition of complex II results in the formation of a Co0.5Ru0.5 solid solution, which is thermodynamically stable under the decomposition conditions. The thermolysis of complexes I and III in a hydrogen atmosphere leads to the formation of metastable solid solutions.