An enzyme-mimic single Fe-N3 atom catalyst for the oxidative synthesis of nitriles via C?C bond cleavage strategy

The cleavage and functionalization of recalcitrant carboncarbon bonds is highly challenging but represents a very powerful tool for value-added transformation of feedstock chemicals. Here, an enzyme-mimic iron single-atom catalyst (SAC) bearing iron (III) nitride (FeN3) motifs was prepared and found to be robust for cleavage and cyana-tion of carbon-carbon bonds in secondary alcohols and ketones. High nitrile yields are obtained with a wide vari-ety of functional groups. The prepared FeN3-SAC exhibits high enzyme-like activity and is capable of generating a dioxygen- to-superoxide radical at room temperature, while the commonly reported FeN4-SAC bearing FeN4 mo-tifs was inactive. Density functional theory (DFT) calculation reveals that the activation energy of dioxygen activa-tion and the activation energy of the rate-determining step of nitrile formation are lower over FeN3-SAC than FeN4-SAC. In addition, DFT calculation also explains the catalyst's high selectivity for nitriles.