Carbon–Nitrogen and Nitrogen–Nitrogen Bond Formation from Nucleophilic Attack at Coordinated Nitrosyls in Fe and Ru Heme Models

The conversion of inorganic NOx species to organo-N compounds is an important component of the global N-cycle. Reaction of a C-based nucleophile, namely the phenyl anion, with the ferric heme nitrosyl [(OEP)­Fe­(NO)­(5-MeIm)]+ generates a mixture of the C-nitroso derivative (OEP)­Fe­(PhNO)­(5-MeIm) and (OEP)­Fe­(Ph). The related reaction with [(OEP)­Ru­(NO)­(5-MeIm)]+ generates the (OEP)­Ru­(PhNO)­(5-MeIm) product. Reactions with the N-based nucleophile diethylamide results in the formation of free diethylnitrosamine, whereas the reaction with azide results in N2O formation; these products derive from attack of the nucleophiles on the bound NO groups. These results provide the first demonstrations of C–N and N–N bond formation from attack of C-based and N-based nucleophiles on synthetic ferric-NO hemes.