Nitric Oxide Dioxygenation by O₂ Adducts of Manganese Porphyrins

We describe here nitric oxide dioxygenation (NOD) by the dioxygen manganese porphyrin adducts Mn(Por)(η²-O₂) (Por^2- = the meso-tetra-phenyl or meso-tetra-p-tolylporphyrinato dianions, TPP^2- and TTP^2-). The Mn(Por)(η²-O₂) was assembled by adding O₂ to sublimed layers of Mn^II(Por). When NO was introduced and the temperature was slowly raised from 80 to 120 K, new IR bands with correlated intensities grew concomitant with depletion of the υ(O₂) band. Isotope labeling experiments with ¹⁸O₂, ¹⁵NO, and N¹⁸O combined with DFT calculations provide the basis for identifying the initial intermediates as the six-coordinate peroxynitrito complexes (ON)Mn(Por)(η¹-OONO). Further warming to room temperature led to formation of the nitrato complexes Mn(Por)(η¹-ONO₂), thereby demonstrating the ability of these metal centers to promote NOD. However, comparable quantities of the nitrito complexes Mn(Por)(η¹-ONO) are also formed. In contrast, when the analogous reactions were initiated with the weak σ-donor ligand tetrahydrofuran or dimethyl sulfide present in the layers, formation of Mn(Por)(η¹-ONO₂) is strongly favored (∼90%). The latter are formed via a 6-coordinate intermediate (L)Mn(Por)(η¹-ONO₂) (L = THF or DMS) that loses L upon warming. These reaction patterns are compared to those observed previously with analogous iron and cobalt porphyrin complexes.