Unusual formation of Ir(III) complexes with non‐symmetrical NacNac ligands: Synthesis, characterization, and evaluation of catalytic activity in transfer hydrogenation reduction reactions

A new type of trans‐ dichloro‐Ir(III) complexes derived from non‐symmetrical NacNac‐type ligands was unexpectedly obtained as the main reaction product from the former ligands and the dimeric species [Ir(COD)Cl 2 ]. One equivalent of LH was reacted with an excess of [Ir(COD)Cl] 2 in dichloromethane or toluene as solvent and at room temperature. The general formula of the product is [IrCl 2 (COD)L] and was isolated as a sole product instead of the expected Ir(I) compound [Ir(COD)L]; all the new Ir(III) were prepared in high yields as microcrystalline solids. They were all stable under laboratory atmosphere, lasting for weeks in solution and for months in solid state. The structure of each compound was examined by 1D and 2D nuclear magnetic resonance (NMR) and high‐resolution mass spectrometry (HRMS). Complex 1k was selected for an X‐ray diffraction study. Finally, an evaluation was made of the catalytic activity of all complexes in the transfer hydrogenation reaction of ketones and imines.