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

Abstract

The tuning of metal-metal interactions in multinuclear assemblies is ac hallenge.S elective Pcoordination of ar edox-active PNO ligand to Au I followed by homoleptic metalation of the NO pocket with Ni II affords au nique trinuclear Au-Ni-Auc omplex. This species features two antiferromagnetically coupled ligand-centered radicals and ad ouble intramolecular d 8 -d 10 interaction, as supported by spectroscopic,s ingle-crystal X-ray diffraction, and computational data. Ac orresponding cationic dinuclear Au-Nia nalogue with as tronger d 8 -d 10 interaction is also reported. Although both heterobimetallic structures displayrich electrochemistry,o nly the trinuclear Au-Ni-Auc omplex facilitates electrocatalytic CÀXb ond activation of alkyl halides in its doubly reduced state.H ence,t he presence of ar edox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. Figure 1. Ligand-through-metal-to-metal communication induced by aligand-based redox process.