An Electron-Deficient Cp-E Iridium(III) Catalyst: Synthesis, Characterization, and Application to Ether-Directed C-H Amidation

The synthesis, characterization, and catalytic performance of an iridium(III) catalyst with an electron-deficient cyclopentadienyl ligand ([(CpIrI2)-Ir-E](2)) are reported. The [(CpIrI2)-Ir-E](2) catalyst was synthesized by complexation of a precursor of the Cp-E ligand with [Ir(cod)OAc](2), followed by oxidation, desilylation, and removal of the COD ligand. The electron-deficient [(CpIrI2)-Ir-E](2) catalyst enabled C-H amidation reactions assisted by a weakly coordinating ether directing group. Experimental mechanistic studies and DFT calculations suggested that the high catalytic performance of [(CpIrI2)-Ir-E](2) is due to its electron-deficient nature, which accelerates both C-H activation and Ir-V-nitrenoid formation.