A novel mechanistic insight for the interconversion between two octahedral ruthenium isomers, trans–mer-[Ru^IICl₂(bpea)(dmso)], 2a, and cis–fac-[Ru^IICl₂(bpea)(dmso)], 2b, (bpea = N,N-bis(2-pyridylmethyl)ethylamine) is reported. The isomer 2a displaying the bpea ligand in a meridional fashion is kinetically favoured with respect to 2b, with the bpea ligand in a facial fashion, which is the thermodynamically favoured one. The dissociative mechanism with the cleavage of a chloro ligand as starting point becomes more feasible with respect to the intramolecular mechanism. However, DFT calculations make competitive the mechanism which dissociates first the dmso ligand. Thus, a further characterisation of all the reaction pathways for the interconversion 2a to 2b has been fulfilled.