Reaction of an oxoiron(IV) complex with nitrogen monoxide: oxygen atom or oxide(•1-) ion transfer?

Reaction of [FeO(tmc)(OAc)](+) with the free radical nitrogen monoxide afforded a mixture of two Fe(II) complexes, [Fe(tmc)(OAc)](+) and [Fe(tmc)(ONO)](+) (where tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and AcO(-) = acetate anion). The amount of nitrite produced in this reaction (ca. 1 equiv with respect to Fe) was determined by ESI mass spectrometry after addition of (15)N-enriched NaNO(2). In contrast to oxygen atom transfer to PPh(3), the NO reaction of [FeO(tmc)(OAc)](+) proceeds through an Fe(III) intermediate that was identified by UV-vis-NIR spectroscopy and ESI mass spectrometry and whose decay is dependent on the concentration of methanol. The observations are consistent with a mechanism involving oxide(•1-) ion transfer from [FeO(tmc)(OAc)](+) to NO to form an Fe(III) complex and NO(2)(-), followed by reduction of the Fe(III) complex. Competitive binding of AcO(-) and NO(2)(-) to Fe(II) then leads to an equilibrium mixture of two Fe(II)(tmc) complexes. Evidence for the incorporation of oxygen from the oxoiron(IV) complex into NO(2)(-) was obtained from an (18)O-labeling experiment. The reported reaction serves as a synthetic example of the NO reactivity of biological oxoiron(IV) species, which has been proposed to have physiological functions such as inhibition of oxidative damage, enhancement of peroxidase activity, and NO scavenging.