Synthesis and Molecular Structure of a Nitrido(porphyrinato)chromium(V) Complex

Irradiation of solutions of azido(5,10,15,20-tetra-p-tolylporphyrinato)chromium(III) in methylene chloride or benzene gave nitrido(5,10,15,20-tetra-p-tolylporphyrinato)chromium(V) (1) in yields of 59% and 82%, respectively. Solutions of 1 showed well-resolved EPR spectra at room temperature (g = 1.985, Anc, = 2.85 mT, /1N = 0.279 mT). The IR spectra of nitrido(5,10,15,20-tetra-p-tolylporphyrinato)chromium(V) (1) and 1-15/V showed bands at 1017 and 991 cm”1, which were assigned to yCl=i4N and vCi=i5Ni respectively. The molecular structure of 1-C6H6 indicated a chromium-nitrogen distance of 1.565 Á, with the chromium 0.42 Á above the mean plane of the pyrrole nitrogens. The periphery of the porphyrin ring was saddle-shaped with excursions 0.56 Á below and 0.29 Á above the plane of the pyrrole nitrogens.