Spectral study of the reactions of dimethyl sulfoxide with the nitrite complexes of Co-porphyrins

It is revealed by FTIR and electron absorption spectroscopy that the reactions of dimethyl sulfoxide with the nitro complexes of Co-porphyrins both in the solid phase and an inert solvent afford six-coordinate complexes with the general formula (DMSO)Со(Por)(NO₂) (Por is meso-tetraphenyl- and meso-tetra-p-tolylporphyrinato dianions). These compounds are stable in the solid state, whereas they partially decompose in an inert solvent to form five- and six-coordinate complexes. The ambident nitrite and dimethyl sulfoxide ligands are coordinated to the metal atom through the N and O atoms, respectively, which was confirmed by the application of isotope-containing compounds ¹⁵NO₂ and DMSO-d₆.