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 (N 2 S 2 )Co III (NO - ), N 2 S 2 = N,N- dibenzyl-3,7-diazanonane-1,9-dithiolate, is introduced as ligand to a well-characterized labile [Ni 0 (NO) + ] synthon. The reaction between [Ni 0 (NO + )] and [Co III (NO - )] has led to a remarkable electronic and ligand redistribution to form a heterobimetallic dinitrosyl cobalt [(N 2 S 2 )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 N 2 S 2 ligand binding site. To date, this is the first reported heterobimetallic cobalt dinitrosyl complex.