IR Study of the Interaction of Dioxygen with [meso-Triphenyl(4-pyridyl)porphyrinato]cobalt(II)

Kurtikyan, Tigran S., Ogden, J. Steven, Kazaryan, Robert K. and Madakyan, Valery N. (2003) IR Study of the Interaction of Dioxygen with [meso-Triphenyl(4-pyridyl)porphyrinato]cobalt(II). European Journal of Inorganic Chemistry, (10), 1861-1865. (doi:10.1002/ejic.200200628).

Abstract

The interaction of O2 (18O2) with [meso-triphenyl(4-pyridyl)porphyrinato]cobalt(II) [Co(MPyTPP)] has been investigated by means of IR spectroscopy under matrix-isolation conditions and by the action of dioxygen on thin sublimed layers. These studies have led to the characterisation of two dioxygen adducts: (1) a very unstable dioxygen adduct similar to that observed earlier for the closely related [meso-tetraphenylporphyrinato]cobalt(II) Co(TPP), and (2) a new type of coordinated O2 (18O2) complex which is formed after warming Co(MPyTPP) either in pure oxygen matrices, or as sublimed layers in the presence of oxygen. The ?(O2) vibration in this second species is more than 100 cm-1 lower than in the first, and the dioxygen adduct thus formed is thermally stable at 200 K. This adduct is identified as a six-coordinate dioxygen complex, with one coordination site occupied by the pyridyl group of an adjacent Co(MPyTPP) molecule. In the sublimed layers, the capacity for self-assembly of Co(MPyTPP) oligomers leads to the formation of microporous solids containing coordinatively unsaturated metal ions which have the ability to bind oxygen reversibly upon storage at ambient conditions.

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