Water-Gas Shift Catalyzed by Iridium-Vanadium Oxide Clusters IrVO₂^-with Iridium in a Rare Oxidation State of -II

The discovery of compounds containing transition metals with an unusual and well-established oxidation state is vital to enrich our horizon on formal oxidation state. Herein, benefiting from the study of the water-gas shift reaction (CO + H₂O → CO₂+ H₂) mediated with the iridium-vanadium oxide cluster IrVO₂^-, the missing -II oxidation state of iridium was identified. The reactions were performed by using our newly developed double ion trap reactors that can spatially separate the addition of reactants and are characterized by mass spectrometry and quantum-chemical calculations. This finding makes an important step that all the proposed 13 oxidation states of iridium (+IX to -III) have been known. The iridium atom in the IrVO₂^-cluster features the Ir═V double bond and resembles chemically the coordinated oxygen atom. A reactivity study demonstrated that the flexible role switch of iridium between an oxygen-atom like (Ir^-IIVO₂^-) and a transition-metal-atom like behavior (Ir^+IIVO₃^-) in different species can drive the water-gas shift reaction in the gas phase under ambient conditions. This result parallels and well rationalizes the extraordinary reactivity of oxide-supported iridium single-atom catalysts in related condensed-phase reactions.