Ruthenium(iii) complexes are known for their high stability and inertness. To the best of our knowledge, the only well-characterized example of a labile Ru(iii) complex is [RuIII(edta)(H2O)] as a consequence of an intramolecular hydrogen bonding leading to the formation of a large opening in the molecule front, thus changing the mechanism from dissociative to associative. Compelling experimental evidence is presented demonstrating that the [RuIII(phtpy)Cl3] complex is labile, also indicating that the Ru(iii)-phtpy bond is much weaker than expected, in contrast to the strongly π-back-bonding stabilized Ru(ii)-phtpy bond.