Three complexes based on an Ir-M (M = Fe, Co, and Ni) heterobimetallic core and 2-(diphenylphosphino)pyridine (PhPPy) ligand were synthesized via the reaction of trans-[IrCl(CO)(PhPPy)] and the corresponding metal chloride. Their structures were established by single-crystal X-ray diffraction as [Ir(CO)(μ-Cl)(μ-PhPPy)FeCl]·2CHCl (2), [IrCl(CO)(μ-PhPPy)CoCl]·2CHCl (3), and [Ir(CO)(μ-Cl)(μ-PhPPy)NiCl]·2CHCl (4). Time-dependent DFT computations suggest a donor-acceptor interaction between a filled 5d orbital on iridium and an empty orbital on the first-row metal atom, which is supported by UV-vis studies. Magnetic moment measurements show that the first-row metals are in their high-spin electronic configurations. Cyclic voltammetry data show that all the complexes undergo irreversible decomposition upon either reduction or oxidation. Reduction of 4 proceeds through an ECE mechanism. While these complexes are not stable to electrocatalysis conditions, the data presented here refine our understanding of the bonding synergies of the first-row and third-row metals.
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