Metal–Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox‐Active Ligands

Abstract

AbstractThe tuning of metal–metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox‐active PNO ligand to AuI followed by homoleptic metalation of the NO pocket with NiII affords a unique trinuclear Au–Ni–Au complex. This species features two antiferromagnetically coupled ligand‐centered radicals and a double intramolecular d8–d10 interaction, as supported by spectroscopic, single‐crystal X‐ray diffraction, and computational data. A corresponding cationic dinuclear Au–Ni analogue with a stronger d8–d10 interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au–Ni–Au complex facilitates electrocatalytic C−X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox‐active ligand framework, an available coordination site at gold, and the nature of the nickel–gold interaction appear to be essential for this reactivity.