The electrochemical reactivity of the first synthesized a-bonded metalloporphycenes is reported. The investigated compounds are represented as (EtioPc)M(C6H5) where M = Fe or In and EtioPc = the dianion of 2,7,12,17-tetraethyl-3,6,13,16-tetramethylporphycene Each compound was examined as to its redox properties in dichloromethane, benzonitrile, or pyridine, and the results of these studies are compared to data for (EtioPc)FeCl and (EtioPc)In(C6H5) under similar solution conditions. Both sigma-bonded derivatives undergo two one-electron reductions at the conjugated pi ring system. This was expected in the case of indium but not in the case of iron which is the first reported example where a monomeric iron(m) porphyrin-like molecule is reduced at the ring rather than at the metal center. (EtioPc)Fe(C6H5) also undergoes three one-electron oxidations, similar to what has been reported for (OETPP)Fe(C6H5) where OETPP is the dianion of octaethyltetraphenylporphyrin. The first oxidation of(EtioPc)Fe(C6H5) occurs at the iron center to give [(EtioPc)Fe-IV(C6H5)](+), which is characterized by UV-visible spectroscopy prior to migration of the phenyl group and demetalation to give (N-C(6)H(5)EtioPc)H as a final product. Assignments of the electron transfer sites for oxidation and reduction of (EtioPc)Fe(C6H5) are based both on spectroelectrochemical data for this compound and on comparison of its electrochemical behavior to that of (EtioPc)FeCl and (EtioPc)In(C6H5).