Aqueous solutions of iridium(III) tetra-(p-sulfonatophenyl)porphyrin [(TSPP)Ir-III]form a hydrogen ion dependent equilibrium distribution of bisaquo (RTSPP)Ir-III(OD2)(2)](3-)), monoaquo/monohydroxo (RTSPP)Ir-III(OD2)(OD)(4-)) and bishydroxo (RTSPP)Ir-III(OD2)(5-)) complexes. Comparison of acid dissociation constants of group nine (RTSPP)M-III(OD2)(2)](3-)) (M = Co, Rh, Ir) complexes show that the extent of proton dissociation in water increases regularly on moving down the group from cobalt to iridium consistent with increasing metal ligand bond strength. Addition of small quantities of methanol to aqueous solutions of [(TSPP)Ir-III] results in the formation of methanol and met hoxide complexes in equilibria with aquo and hydroxo complexes that are observed by H-1 NMR. Direct quantitative evaluation of competitive equilibria of [(TSPP)Ir-III] complexes reveals a remarkable thermodynamic preference for methanol binding over that of water (Delta G degrees (298 K) = 5.2 kcal mol(-1)) and methoxide binding over that of hydroxide (Delta G degrees (298 K) = 6.1 kcal mol(-1)) in aqueous media. A comparison of equilibrium thermodynamic values for displacement of hydroxide by methoxide for group nine (TSPP)M-III (M = Co, Rh, Ir) complexes in aqueous media are also reported.