Organometallic-polyoxometalate (POM) complexes form a unique class of molecular organometallic oxides characterized by the dynamic behavior of the organometallic cations. Herein, we investigated the reactivity of Cp*Ir-octatungstate clusters (where Cp* represents pentamethylcyclopentadienyl, CMe) with Werner-type transition-metal aquo cations. The addition of Ag, Co, Ni, and M (M = Cr, Fe, or In) cations to the aqueous solution of Cp*Ir-octatungstate clusters resulted in the formation of [{Ag(OH)}{Cp*Ir(OH)}{Cp*IrWO(OH)}(WO)] (), CoKNa[{-Co(OH)}{Cp*IrWO(OH)}(WO){-Co(OH)}] (), NiKNa[{Ni(OH)}{Cp*IrWO(OH)}(WO){-Ni(OH)}] (), and [{M(OH)}{Cp*IrWO(OH)}{-M(OH)}](NO) (M = Cr, ; Fe, ; or In, ), respectively. All clusters share the same cubane-type {Cp*IrWO(OH)} building block, representing the first examples of organoiridium-POMs functionalized by transition-metal aquo cations. These compounds are insoluble in water, facilitating the evaluation of their heterogeneous water-oxidation properties. Notably, generates the highest catalytic water oxidation current. This work provides a new synthetic method to introduce metal-aquo complexes on an organometallic oxide cluster, producing multimetallic molecules that model the catalytic sites of complex oxides.
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