Preparation and spectroscopic properties of the (cyanato-N) and (oxalato) iron(III) “picket fence” porphyrins: Structure of the (cyanato-N)(α,α,α,α-tetrakis(<i>o</i>-pivalamidophenyl)porphinato)iron(III) complex

Abstract

The reaction of the iron(III) aqua triflato picket fence porphyrin starting material with NaOCN and K 2 C 2 O 4 salts, solubilized by the crown ether 18- C -6 in organic solvents, yields respectively the iron(III) porphyrin species [ Fe III ( TpivPP )( NCO )] and [ Fe III ( TpivPP )( ox )] − . These compounds have been characterized by UV-vis, IR, and 1 H NMR spectroscopies. Proton NMR data for the isolated products are in accordance with high-spin ( S = 5/2) ferric porphyrin derivatives. The X-ray molecular structure of the (cyanato-N)(α,α,α,α-tertakis(o-pivalamidophenyl)porphinato)iron(III), has been determined. This structure, which is the first one reported of an iron-cyanato species, confirms the spin-state of the cyanato derivative. The iron atom is pentacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atom of the NCO − group. It lies at 0.540(1) Å out of the porphinato plane and 0.486(1) Å out of the four nitrogen plane of the porphyrin ring. The Fe – N ( NCO ) bond length is 1.970(2) Å and the Fe - N - C ( NCO ) bond angle is 169.9(3)°.