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

With the goal of generating hetero-redox levels on metals as well as on nitric oxide (NO), metallodithiolate (N2 S2 )CoIII (NO- ), N2 S2 = 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 [CoIII (NO- )] has led to a remarkable electronic and ligand redistribution to form a heterobimetallic dinitrosyl cobalt [(N2 S2 )NiII ∙Co(NO)2 ]+ complex with formal two electron oxidation state switches concomitant with the nickel extraction or transfer as NiII into the N2 S2 ligand binding site. To date, this is the first reported heterobimetallic cobalt dinitrosyl complex.