Mechanism of the catalytic reduction of nitric oxide with ammonia by a solution of dinitro-(alkyldiamine) CoIII complexes

Abstract

It is demonstrated that the reduction of nitric oxide by dinitro-(alkyldiamine) Co^III complexes proceeds through the dissociation of the amine group of the alkyldiamine ligand, followed by the formation of mononitrosyl and dinitrosyl intermediate complexes from which N₂ and N₂O are produced, respectively.

In aqueous solution, the coordination of NO and NH₃ to the catalytically active intermediate complex is the rate-determining step, which shifts to the reaction of coordinated nitric oxide with ammonia in DMF solution. The stabilities of these intermediate complexes depend on the structure of the alkyldiamine ligands, which cause different selectivities for N₂ and N₂O formation.