Bond Trading: Intramolecular Metal and Ligand Exchange within a NO/Ni/Co Complex

Abstract With the goal of generating hetero‐redox levels on metals as well as on nitric oxide (NO), metallodithiolate (N₂S₂)Co^III(NO⁻), N₂S₂ = N,N‐ dibenzyl‐3,7‐diazanonane‐1,9‐dithiolate, is introduced as ligand to a well‐characterized labile [Ni⁰(NO)⁺] synthon. The reaction between [Ni⁰(NO⁺)] and [Co^III(NO⁻)] has led to a remarkable electronic and ligand redistribution to form a heterobimetallic dinitrosyl cobalt [(N₂S₂)Ni^II∙Co(NO)₂]⁺ complex with formal two electron oxidation state switches concomitant with the nickel extraction or transfer as Ni^II into the N₂S₂ ligand binding site. To date, this is the first reported heterobimetallic cobalt dinitrosyl complex.