An IrVO₄⁺ Cluster Catalytically Oxidizes Four CO Molecules: Importance of Ir-V Multiple Bonding

The generation and characterization of multiple metal-metal (M-M) bonds between early and late transition metals is vital to correlate the nature of multiple M-M bonds with the related reactivity in catalysis, while the examples with multiple M-M bonds have been rarely reported. Herein, we identified that the quadruple bonding interactions were formed in a gas-phase ion IrV⁺ with a dramatically short Ir-V bond. Oxidation of four CO molecules by IrVO₄⁺ is a highly exothermic process driven by the generation of stable products IrV⁺ and CO₂, and then IrV⁺ can be oxidized by N₂O to regenerate IrVO₄⁺. This finding overturns the general impression that vanadium oxide clusters are unwilling to oxidize multiple CO molecules because of the strong V-O bond and that at most two oxygen atoms can be supplied from a single V-containing cluster in CO oxidation. This study emphasizes the potential importance of heterobimetallic multiple M-M bonds in related heterogeneous catalysis.