The spin states of the iron(III) complexes with a highly ruffled porphyrin ring, [Fe(TEtPrP)X] where X = F-, Cl-, Br-, I-, and ClO4, have been examined by 1H NMR, C-13 NMR, EPR, and Mossbauer spectroscopy. While the F Cl-, and Br- complexes adopt a high-spin (S = 112) state, the I- complex exhibits an admixed intermediate-spin (S = 5/2, 3/2) state in CD2Cl2 solution. The I- complex shows, however, a quite pure high-spin state in toluene solution as well as in the solid. The results contrast those of highly saddled [Fe(OETPP)X] where the I-complex exhibits an essentially pure intermediate-spin state both in solution and in the solid. In contrast to the halide-ligated complexes, the ClO4- complex shows a quite pure intermediate-spin state. The 13 C NMR spectra of [Fe(TEtPrP)ClO4] are characterized by the downfield and upfield shifts of the meso and pyrrole-alpha(x carbon signals, respectively: delta(meso) = +342 and delta(alpha-py) = -287 ppm at 298 K. The data indicate that the meso carbon atoms of [Fe(TEtPrP)ClO4] have considerable amounts of positive spin, which in turn indicate that the iron has an unpaired electron in the d(xy) orbital; the unpaired electron in the d(xy) orbital is delocalized to the meso positions due to the iron(d(xy))-porphyrin(a(2u)) interaction. Similar results have been obtained in analogous [Fe((TPrP)-Pr-i)X] though the intermediate-spin character of [Fe((TPrP)-Pr-i)X] is much larger than that of the corresponding [Fe(TEtPrP)X]. On the basis of these results, we have concluded that the highly ruffled intermediate-spin complexes such as [Fe(TEtPrP)ClO4] and [Fe((TPrP)-Pr-i)ClO4] adopt a novel (d(xz), d(yz))(3)(d(xy))(1)(d(z)(2))(1) electron configuration; the electron configuration of the intermediate-spin complexes reported previously is believed to be (d(xy))(2)(d(xz), d(yz))(2)(d(z)(2))(1).