6533b81ffe1ef96bd1278f8c

RESEARCH PRODUCT

Physicochemical Characterization of σ-Bonded Aryl Iron(III) Porphycenes. X-ray Structures of (EtioPc)Fe(3,5-C6F2H3) and (EtioPc)In(C6H5), Where EtioPc Is the Dianion of 2,7,12,17-Tetraethyl-3,6,13,16-tetramethylporphycene

subject

description

A series of iron(III) σ-bonded porphycenes are characterized by their electrochemical and spectroscopic properties. The investigated compounds are represented as (EtioPc)Fe(R), where EtioPc = the dianion of 2,7,12,17-tetraethyl-3,6,13,16-tetramethylporphycene and R = C6H5, 3,5-C6F2H3, 3,4,5-C6F3H2 or 2,3,5,6-C6F4H. Each compound is characterized as to its ESR, NMR, and UV−visible properties which are compared to corresponding compounds in an analogous series of (OEP)Fe(R) and (OETPP)Fe(R) derivatives where OEP and OETPP are the dianions of octaethyl- and octaethyltetraphenylporphyrin, respectively. The (EtioPc)Fe(R) complexes contain either high- or low-spin Fe(III), depending on the specific axial ligand and the temperature. The first oxidation of each (EtioPc)Fe(R) complex involves a metal-centered reaction while the other electron transfers involve the addition or abstraction of electrons from the conjugated π-ring system of the porphycene. An X-ray crystal structure of low-spin (EtioPc)Fe(3,5-C6F2H3) ...