Interaction of NO2 gas with sublimed microporous layers of iron(II)-meso-mono-4-pyridyl-tri-aryl-porphyrins: Two different reaction pathways

Sublimed layers of Fe II MPyTPP and Fe II MPyTTP ( MPyTPP and MPyTTP are meso-mono-4-pyridyl-triphenyl- and meso-mono-4-pyridyl-tri-p-tolyl-porphyrin dianions, respectively) consist of coordination oligomers that are formed by binding of pyridyl nitrogen atoms with the iron centers of the adjacent molecules in the film. Fourier transform infrared (FT-IR) spectroscopy including experiments with the 15 NO 2 isotopomer demonstrates that the reaction of low pressure NO 2 gas with these layers leads to the formation of two types of complexes: six-coordinate nitro-complexes, in which the fifth site is occupied by the pyridyl group of the neighboring molecule in the layer and five-coordinate nitrito-complexes that terminate the oligomers. Further addition of NO 2 increments leads to the preferential oxidation of these nitrito ligands to bidentate nitrato ligands. These layers conserve their porosity upon standing and allow study of the oxo-transfer reactivity from coordinated nitro-groups to appropriate oxygen acceptors.