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The pH-dependent binding strengths and modes of the organometallic [(η⁶-<i>p</i>-cym)M(H₂O)₃]²⁺ (M^II = Ru, Os; <i>p</i>-cym = 1-methyl-4-isopropylbenzene) or [(η⁵-Cp*)M(H₂O)₃]²⁺ (M^III = Rh, Ir; Cp* = pentamethylcyclopentadienyl anion) cations towards iminodiacetic acid (H₂Ida) and its biorelevant mono- and diphosphonate derivatives N-(phosphonomethyl)-glycine (H₃IdaP) and iminodi(methylphosphonic acid) (H₄Ida2P) was studied in an aqueous solution. The results showed that all three of the ligands form 1:1 complexes via the tridentate (O,N,O) donor set, for which the binding mode was further corroborated by the DFT method. Although with IdaP³⁻ and Ida2P⁴⁻ in mono- and bis-protonated species, where H⁺ might also be located at the non-coordinating N atom, the theoretical calculations revealed the protonation of the phosphonate group(s) and the tridentate coordination of the phosphonate ligands. The replacement of one carboxylate in Ida²⁻ by a phosphonate group (IdaP³⁻) resulted in a significant increase in the stability of the metal complexes; however, this increase vanished with Ida2P⁴⁻, which was most likely due to some steric hindrance upon the coordination of the second large phosphonate group to form (5 + 5) joined chelates. In the phosphonate-containing systems, the neutral 1:1 complexes are the major species at pH 7.4 in the millimolar concentration range that is supported by both NMR and ESI-TOF-MS.