Fe(II), Fe(I) and Fe(0) porphyrins have been generated by stepwise reduction with a sodium mirror in vacuum and their 1H NMR spectra have been recorded and analyzed. Fe(II) porphyrins (Fe(II)P) have been examined in three spin states, an S = 0 state in pyridine- d 8, an S = 1 state in benzene- d 6 and an S = 2 state in tetrahydrofuran- d 8 (THF- d 8). The analysis of isotropic shifts for low-spin Fe(II)P ( S = 0) has indicated that no charge transfer has been observed. The ground state configuration is (d xy) 2 (d xz,d yx) 4. The contact shifts for intermediate-spin Fe(II)P ( S = 1) reflect P → Fe π charge transfer. The proposed electron configuration is (d xy) 2 (d z2) 2 (d xz, d yz) 2, which agrees with Mössbauer data. The pattern of contact shifts for high-spin Fe(II)P ( S = 2) is consistent with σ spin transfer, which suggests that the d x2-y2 orbital possesses an unpaired spin. The electron configuration is (d xy) 2 (d xz, d yz 2 (d z2) 1 (d x2-y2) 1. Our results for Fe(II)P ( S = 1,2) agree with the literature 1H NMR data . In the case of Fe(I)P in THF, the separation of isotropic shifts into the dipolar and contact contributions has shown the dominance of the latter. The observed shifts indicate negative π spin density on pyrrole and meso carbon atoms of the ligand, which seems to be due to a strong π-π spin polarization effect. When this fact is taken into account the pattern of contact shifts is consistent with π spin transmission involving both P → Fe π charge transfer out of the ligand-filled molecular (3e(π)) orbital and Fe → P π * charge transfer into the ligand highest unoccupied (4e(π *)) molecular orbital. The occurrence of the unpaired spin in this molecular orbital is consistent with π-radical anion formulation which was found by X-ray crystallography. An S = 1/2 spin state determined by magnetic moment measurements agrees with the most probable electron configuration (d xy) 2 (d xz, d yz 3 (d z2) 2. In the case of Fe(0)P, the isotropic shifts were found to be small, providing evidence of some spin transfer. The ground state configuration is (d xy) 2 (d xz, d yz) 4 (d z2) 2.
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