Advanced Paramagnetic Resonance Studies on Manganese and Iron Corroles with a Formal d⁴ Electron Count

Metallocorroles wherein the metal ion is Mn^III and formally Fe^IV are studied here using field- and frequency-domain electron paramagnetic resonance techniques. The Mn^III corrole, Mn(tpfc) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole trianion), exhibits the following S = 2 zero-field splitting (zfs) parameters: D = -2.67(1) cm^-1, |E| = 0.023(5) cm^-1. This result and those for other Mn^III tetrapyrroles indicate that when D ≈ - 2.5 ± 0.5 cm^-1 for 4- or 5-coordinate and D ≈ - 3.5 ± 0.5 cm^-1 for 6-coordinate complexes, the ground state description is [Mn^III(Cor^3-)]⁰ or [Mn^III(P^2-)]⁺ (Cor = corrole, P = porphyrin). The situation for formally Fe^IV corroles is more complicated, and it has been shown that for Fe(Cor)X, when X = Ph (phenyl), the ground state is a spin triplet best described by [Fe^IV(Cor^3-)]⁺, but when X = halide, the ground state corresponds to [Fe^III(Cor^•2-)]⁺, wherein an intermediate spin (S = ³/₂) Fe^III is antiferromagnetically coupled to a corrole radical dianion (S = ¹/₂) to also give an S = 1 ground state. These two valence isomers can be distinguished by their zfs parameters, as determined here for Fe(tpc)X, X = Ph, Cl (tpc = 5,10,15-triphenylcorrole trianion). The complex with axial phenyl gives D = 21.1(2) cm^-1, while that with axial chloride gives D = 14.6(1) cm^-1. The D value for Fe(tpc)Ph is in rough agreement with the range of values reported for other Fe^IV complexes. In contrast, the D value for Fe(tpc)Cl is inconsistent with an Fe^IV description and represents a different type of iron center. Computational studies corroborate the zfs for the two types of iron corrole complexes. Thus, the zfs of metallocorroles can be diagnostic as to the electronic structure of a formally high oxidation state metallocorrole, and by extension to metalloporphyrins, although such studies have yet to be performed.