Details

Autor(en) / Beteiligte

• Kurtikyan, Tigran S
• Gulyan, Gurgen M
• Martirosyan, Garik G
• Lim, Mark D
• Ford, Peter C

Titel

Reactions of Nitrogen Oxides with Heme Models. Spectral and Kinetic Study of Nitric Oxide Reactions with Solid and Solute FeIII(TPP)(NO3)

Ist Teil von

• Journal of the American Chemical Society, 2005-05, Vol.127 (17), p.6216-6224

Ort / Verlag

Washington, DC: American Chemical Society

Erscheinungsjahr

2005

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The reaction(s) of nitric oxide (nitrogen monoxide) gas with sublimed layers containing the nitrato iron(III) complex FeIII(TPP)(η2-O2NO) (1, TPP = meso-tetraphenyl porphyrinate2-) leads to formation of several iron porphyrin species that are ligated by various nitrogen oxides. The eventual products of these low-temperature solid-state reactions are the nitrosyl complex Fe(TPP)(NO), the nitro-nitrosyl complex Fe(TPP)(NO2)(NO), and 1 itself, and the relative final quantities of these were functions of the NO partial pressure. It is particularly notable that isotope labeling experiments show that the nitrato product is not simply unreacted 1 but is the result of a series of transformations taking place in the layered material. Thus, the nitrato complex formed from solid Fe(TPP)(η2-O2NO) maintained under a 15NO atmosphere was found to be the labeled analogue Fe(TPP)(η2-O2 15NO). The reactivities of the layered solids are compared to the behaviors of the same species in ambient temperature solutions. To interpret the reactions of the labeled nitrogen oxides, the potential exchange reactions between N2O3 and 15NO were examined, and complete isotope scrambling was observed between these species under the reaction conditions (T = 140 K). Overall it was concluded from isotope labeling experiments that the sequence of reactions is initiated by reaction of 1 with NO to give the nitrato nitrosyl complex Fe(TPP)(η1-ONO2)(NO) (2) as an intermediate. This is followed by a reaction in the presence of excess NO that is equivalent to the loss of the nitrate radical NO3 • to give Fe(TPP)(NO) as another transient species. A plausible pathway involving NO attack on the coordinated nitrate of 2 resulting in the release of N2O4 concerted with electron transfer to the metal center is proposed.