The spin states of the iron(III) complexes with a highly ruffled porphyrin ring, [Fe(TEtPrP)X] where X = F-, Cl-, Br-, l-, and ClO4-, have been examined by 1H NMR, 13C NMR, EPR, and Mössbauer spectroscopy. While the F-, Cl-, and Br- complexes adopt a high-spin (S = 5/2) state, the l- complex exhibits an admixed intermediate-spin (S = 5/2, 3/2) state in CD2Cl2 solution. The l- 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 l- 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 13C NMR spectra of [Fe(TEtPrP)-ClO4] are characterized by the downfield and upfield shifts of the meso and pyrrole-α carbon signals, respectively: δ(meso) = +342 and δ(α-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 dxy orbital; the unpaired electron in the dxy orbital is delocalized to the meso positions due to the iron (dxy)-porphyrin(a2u) interaction. Similar results have been obtained in analogous [Fe(TiPrP)X] though the intermediate-spin character of [Fe(TiPrP)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)-ClO 4] and [Fe(TiPrP)ClO4] adopt a novel (d xz, dyz)3(dxy)1(dz 2)1 electron configuration; the electron configuration of the intermediate-spin complexes reported previously is believed to be (d xy)2(dxz, dyz)2(d z2)1.
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