Electronic Structures of Five-Coordinate Iron(III) Porphyrin Complexes with Highly Ruffled Porphyrin Ring

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, 13C NMR, EPR, and Mössbauer spectroscopy. While the F-, Cl-, and Br- complexes adopt a high-spin (S = 5/2) 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 13C NMR spectra of Fe(TEtPrP)ClO4 are characterized by the downfield and upfield shifts of the meso and pyrrole-alpha 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(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)ClO4 and Fe(TiPrP)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.