Coordination of sigma-aryl carbanions by chloroiron(II) 5,20-ditolyl-10,15-diphenyl-21-oxaporphyrin (ODTDPP)(FeCl)-Cl-II has been followed by H-1 NMR spectroscopy. Addition of pentafluorophenyl Grignard reagent (C6F5)MgBr to the toluene solution of (ODTDPP)(FeCl)-Cl-II in the absence of dioxygen at 205 K resulted in the formation of the high-spin (ODTDPP)Fe-II(C6F5). The titration of (ODTDPP)(FeCl)-Cl-II with a solution of (C6H5)MgBr carried at 205 K yields a rare six-coordinate species which binds two sigma-aryl ligands [(ODTDPP)Fe-II(C6H5)(2)](-). Warming of the [(ODTDPP)Fe-II(C6H5)(2)](-) solution above 270 K results in the decomposition to mono-sigma-phenyliron species (ODTDPP)Fe-II(C6H5). Controlled oxidation of [(ODTDPP)Fe-II(C6H5)(2)](-) with Br-2 affords (ODTDPP)Fe-II(C6H5)Br, which demonstrates a typical H-1 NMR pattern of low-spin sigma-aryl iron(III) porphyrin. The considered oxidation mechanism involves the (ODTDPP)Fe-III(C6H5)(2) species, which is readily reduced to the iron(I) 21-oxaporphyrin, followed by oxidation with Br-2 and replacement of one bromide anion by aryl substituent. The H-1 NMR spectra of paramagnetic iron complexes have been examined in detail. Functional group assignments have been made with the use of selective deuteration. The peculiar H-1 NMR spectral features of [(ODTDPP)Fe-II(p-CH3C6H4)(2)](-) (sigma-p-tolyl: ortho, 30.8; meta, 53.6; para-CH3, 42.1; furan: -16.0; beta-H pyrrole: -27.5, -34.3, -41.8 ppm, at 205 K) are without a parallel to any iron(II) porphyrin or heteroporphyrin and indicate a profound alteration of the electronic structure of iron(II) porphyrin upon the coordination of two sigma-aryls.