Reactions of the free radical nitrogen monoxide with metal�oxygen species of metalloproteins are relevant to NO metabolism and detoxification. To gain insight into the fundamental reactivity of oxoiron(IV) complexes in this context, we have investigated the reaction of [FeO(tmc)(OAc)]+ with NO (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). This reaction caused reduction of the FeIV center to FeII and produced nitrite, which was identified in the form of [Fe(tmc)(ONO)]+ using ESI mass spectrometry. An intermediate was observed by UV�visible spectroscopy and ESI mass spectrometry, and evidence for incorporation of the oxo ligand from [FeO(tmc)(OAc)]+ into the nitrite product was obtained from an 18O-labeling experiment. Two possible mechanisms may be considered involving oxygen atom or oxide(�1�) ion transfer from the FeIVO group to NO. In a related reaction, nitrite was also produced by oxidation of the nitrosyl complex [Fe(tmc)(NO)]2+ with trimethylamine N-oxide.

Reactivity of an oxoiron(IV) complex toward nitrogen monoxide

243rd National Meeting (2012)

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