Molar-Ratio-Dependent Coordination Assembly of Organoiridium(III)-Octatungstate Complexes in Aqueous Solution

We scrutinized the speciation of Cp*Ir-containing tungsten oxide clusters (Cp* is pentamethylcyclopentadienyl anion) in aqueous mixtures of [(Cp*IrCl)2(mu-Cl)2] and Na2WO4 in varying molar ratios. 1H nuclear magnetic resonance (NMR) spectroscopy revealed the formation of three distinct Cp*Ir-polyoxotungstate species in the reaction solution, and they were isolated as Na4[(Cp*Ir)2(mu-OH)3]2[(Cp*Ir)2H2W8O30] (1), [(Cp*Ir)2(mu-OH)3]2[(Cp*Ir)2{Cp*Ir(OH2)}2H2W8O30] (2), and [(Cp*Ir)2{Cp*Ir(OH2)}2{Cp*Ir(OH2)2}2H2W8O30](NO3)2 (3) from the mixtures in which iridium concentration is less than, equal to, and more than the tungsten concentration, respectively. These results show the octatungstate [H2W8O30]10- anion is the major polyoxotungstate species in the presence of {Cp*Ir}2+ cations, and it has high nucleophilicity enough to bind up to six {Cp*Ir}2+ cations on its surfaces producing a cationic Cp*Ir- octatungstate complex. The octatungstate anion was also generated from the reaction of [(Cp*IrCl)2(mu-Cl)2] and methylammonium paratungstate-B, (CH3NH3)10[H2W12O42], and was isolated as a methylamine-coordinated complex (CH3NH3)2[(Cp*Ir)2{Cp*Ir-(NH2CH3)}2H2W8O30] (4), indicating {Cp*Ir}2+ cations function as a structure-directing agent that converts tungsten species into octatungstate anions in aqueous solution. In addition, the coordination environment of {Cp*Ir}2+ can be further modified by coordination with pyridine forming [{Cp*Ir(NC5H5)}2(mu-OH)2][(Cp*Ir)2{Cp*Ir(NC5H5)}2H2W8O30] (5).

Automated summary

Through 1H NMR spectroscopy analysis, we identified three distinct Cp*Ir-containing tungsten oxide clusters formed in aqueous mixtures of [(Cp*IrCl)2(mu-Cl)2] and Na2WO4 with varying molar ratios. These species were isolated as Na4[(Cp*Ir)2(mu-OH)3]2[(Cp*Ir)2H2W8O30], [(Cp*Ir)2(mu-OH)3]2[(Cp*Ir)2{Cp*Ir(OH2)}2H2W8O30], and [(Cp*Ir)2{Cp*Ir(OH2)}2{Cp*Ir(OH2)2}2H2W8O30](NO3)2. The results indicate that the octatungstate [H2W8O30]10- anion is the main polyoxotungstate species in the presence of {Cp*Ir}2+ cations, which can bind up to six {Cp*Ir}2+ cations on its surfaces. Moreover, the coordination environment of {Cp*Ir}2+ can be altered by coordinating with pyridine.