Homo‐ and Heterobimetallic Complexes Bearing NHC Ligands: Applications in α‐Arylation of Amide, Suzuki–Miyaura Coupling Reactions, and Tandem Catalysis

A heterobimetallic IrIII/PdII complex from a dicarbene donor ligand featuring cyclometalated IrIII and PEPPSI type PdII is presented along with a homodinuclear PEPPSI type PdII complex starting from the same bis‐imidazolium salt. All the PdII complexes are active precatalyst in both α‐arylation and Suzuki–Miyaura coupling reactions. The heterobimetallic IrIII/PdII complex shows much higher yields in tandem C–C coupling/transfer hydrogenation reactions compared to the equimolar mixture of their mononuclear PdII and IrIII counterparts. A heterobimetallic IrIII/PdII complex from a dicarbene donor ligand featuring cyclometalated IrIII and PEPPSI type PdII is presented along with a homodinuclear PEPPSI type PdII complex starting from the same bis‐imidazolium salt. The heterobimetallic IrIII/PdII complex appears as active precatalyst in tandem catalytic transformations of 4‐bromoabenzaldehyde to 4‐biphenylmethanol derivatives.