Reactivity of Organoiridium Tungsten Oxide Clusters with Transition Metal Aquo Cations

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, C5Me5–) with Werner-type transition-metal aquo cations. The addition of Ag+, Co2+, Ni2+, and M3+ (M = Cr, Fe, or In) cations to the aqueous solution of Cp*Ir-octatungstate clusters resulted in the formation of [{Ag(OH2)2}2{Cp*Ir(OH2)}2{Cp*IrW3O12(OH)}2(WO2)2] (1), Co1.5K0.8Na0.2[{trans-Co(OH2)2}{Cp*IrW3O12(OH)}2(WO2)1.3{cis-Co(OH2)2}0.7] (2-Co), Ni0.2K1.4Na0.2[{Ni(OH2)4}2{Cp*IrW3O12(OH)}2(WO2)1.1{cis-Ni(OH2)2}0.9] (2-Ni), and [{M(OH2)4}2{Cp*IrW3O12(OH)}2{cis-M(OH2)2}2](NO3)2 (M = Cr, 3-Cr; Fe, 3-Fe; or In, 3-In), respectively. All clusters share the same cubane-type {Cp*IrW3O12(OH)}5– 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, 2-Co 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.