Synthesis and redox properties of a [<i>meso</i>-tris(4-nitrophenyl) corrolato]<font>Mn(III)</font> complex

Abstract

The Mn complexated corrole [ T (4- NO 2 P ) Corr ] Mn ( py ) (3) has been prepared ( py = pyridine ) where [ T (4- NO 2 P ) Corr ] is the trianion of the electron-poor 5,10,15-tris(4-nitrophenyl)corrole (1). The preparation of 3 includes a new synthetic method to form the corrole ligand 1 in a two-step synthesis. The Mn(III) complex gives a parallel mode EPR signal centered around g = 8.2 with six distinct hyperfine lines ( A || = 139 × 10 -4 cm -1 ). Electrochemically 3 undergoes one reversible oxidation ( E 1/2 = 0.12 V vs Fc) and two reversible reductions ( E 1/2 = -1.45, -1.61 V). The oxidation is metal-centered and the product has been characterized by EPR spectroscopy as an S = 3/2 Mn(IV) species with no indication for oxidation of the macrocycle. The reductions of complex 3 are ligand based, and at the potential of the second reduction step a stable nitrogen centered radical with g = 2.0055 is generated. Chemical oxidation of 3 by iodosobenzene yields a Mn(IV) complex and epoxidation of cis-stilbene is not catalyzed by the Mn complex.