Oxyfunctionalization with Cp*Ir(III)(NHC)(Me)(Cl) with O₂: identification of a rare bimetallic Ir(IV) μ-oxo intermediate.

Methanol formation from [Cp*Ir(III)(NHC)Me(CD2Cl2)](+) occurs quantitatively at room temperature with air (O2) as the oxidant and ethanol as a proton source. A rare example of a diiridium bimetallic complex, [(Cp*Ir(NHC)Me)2(μ-O)][(BAr(F)4)2], 3, was isolated and shown to be an intermediate in this reaction. The electronic absorption spectrum of 3 features a broad observation at ∼660 nm, which is primarily responsible for its blue color.