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.