High-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopy has been used to study two complexes of high-spin manganese(III), d(4), S = 2. The complexes studied were (tetraphenylporphyrinato)manganese(III) chloride and (phthalocyanato)manganese(III) chloride. Our previous HFEPR study (Goldberg, D. P.; Telser, J.; Krzystek, J.; Montalban, A. G.; Brunel, L.-C.; Barrett, A. G. M.; Hoffman, B. M. J. Ain. Chem. Sec. 1997, 119, 8722-8723) included results on the porphyrin complex; however, we were unable to obtain true powder pattern HFEPR spectra, as the crystallites oriented in the intense external magnetic field. In this work we are now able to immobilize the powder, either in an n-eicosane mull or KBr pellet and obtain true powder pattern spectra. These spectra have been fully analyzed using spectral simulation software, and a complete set of spin Hamiltonian parameters has been determined for each complex. Both complexes are rigorously axial systems, with relatively low magnitude zero-field splitting: D approximate to -2.3 cm(-1) and g values quite close to 2.00. Prior to this work, no experimental nor theoretical data exist for the metal-based electronic energy levels in Mn(III) complexes of porphyrinic ligands. This lack of information is in contrast to other transition metal complexes and is likely due to the dominance of ligand-based transitions in the absorption spectra of Mn(III) complexes of this type. We have therefore made use of theoretical values for the electronic energy levels of (phthalocyanato)copper(II), which electronically resembles these Mn(III) complexes. This analogy works surprisingly well in terms of the agreement between the calculated and experimentally determined EPR parameters. These results show a significant mixing of the triplet (S = I) excited state with the quintet (S = 2) ground state in Mn(III) complexes with porphyrinic ligands. This is in agreement with the experimental observation of lower spin ground states in other metalloporphyrinic complexes, such as those of Fe(II) with S = 1.