Can bis(imino)pyridine iron, (PDI)FeL1L2, complexes catalyze C–H bond functionalization?

Abstract

The DFT approach is used to analyse the mechanism and controlling factors of (PDI)Fe^II(N₂)₂ and (PDI)Fe^IICl(OEt₂) complexes (i.e. a combination of a earth-abundant metal (Fe) and a non-innocent bis(imino)pyridine (PDI) ligand) catalyzed benzylic C–H bond functionalization by unsubstituted and donor–acceptor diazocarbenes. Results suggest that the use of (PDI)FeCl(OEt₂) complex and donor–acceptor carbenes is absolutely necessary for the benzylic C–H bond alkylation. Furthermore, the non-innocent PDI ligand acts as a one-electron oxidant upon formation of the reactive (PDI)Fe(Cl)CR¹R² carbenoid.