Dioxygen Binding to Protonated Heme in the Gas Phase, an Intermediate Between Ferric and Ferrous Heme
Résumé
With a view to characterizing the influence of the electronic structure of the Fe atom on the nature of its bond with dioxygen (O2) in heme compounds, a study of the UV/Vis action spectra and binding energies of heme-O2 molecules has been undertaken in the gas phase. The binding reaction of protonated ferrous heme [FeII-hemeH]+ with O2 has been studied in the gas phase by determining the equilibrium of complexed [FeII-hemeH(O2)]+ with uncomplexed protonated heme in an ion trap at controlled temperatures. The binding energy of O2 to the Fe atom of protonated ferrous heme was obtained from a van't Hoff plot. Surprisingly, this energy (1540±170 cm−1, 18.4±2 kJ mol−1) is intermediate between those of ferric heme and ferrous heme. This result is interpreted in terms of a delocalization of the positive charge over the porphyrin cycle, such that the Fe atom bears a fractional positive charge. The resulting electron distribution on the Fe atom differs notably from that of a purely low-spin ferrous heme [FeII-heme(O2)] complex, as deduced from its absorption spectrum. It also differs from that of ferric heme [FeIII-heme(O2)]+, as evidenced by the absorption spectra. Protonated heme creates a specific bond that cannot accommodate strong σ donation.