Redox‐Active Ligand‐Induced Homolytic Bond Activation

Coordination of the novel redox-active phosphine-appended aminophenol pincer ligand (PNO(H2) ) to Pd(II) generates a paramagnetic complex with a persistent ligand-centered radical. The complex undergoes fully reversible single-electron oxidation and reduction. Homolytic bond activation of diphenyldisulfide by the single-electron reduced species leads to a ligand-based mixed-valent dinuclear palladium complex with a single bridging thiolate ligand. Mechanistic investigations support an unprecedented intramolecular ligand-to-disulfide single-electron transfer process to induce homolytic SS cleavage, thereby releasing a thiyl (sulfanyl) radical. This could be a new strategy for small-molecule bond activation.