Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand

► Linkage isomerism between N-bound nitrate and O-bound nitrate on the oxo-acetato triruthenium is affected by ancillary ligand. ► The [Ru3O(CH3CO2)6(NO2)(dmap)2] is obtained as a single isomer having N-bound nitrate, whereas the [Ru3O(CH3CO2)6(NO2)(py)2] is obtained as a mixture of linkage isomers, having N-bound nitrate and O-bound nitrate. ► X-ray crystallography of [Ru3O(CH3CO2)6(NCS)(C5H5N)2]·2CH2Cl2 reveals that the NCS coordinates linearly, and the triangle formed by the three rutheniums is almost equilateral. ► The first example of oxo-carboxylato triruthenium complex with negative charge.