Synthesis, Spectral Characterization, Structures, and Oxidation State Distributions in [(corrolato)Fe^III(NO)]^<i>n</i> (<i>n</i> = 0, +1, −1) Complexes

Two novel <i>trans</i>-A₂B-corroles and three [(corrolato)­{FeNO}⁶] complexes have been prepared and characterized by various spectroscopic techniques. In the native state, all these [(corrolato)­{FeNO}⁶] species are diamagnetic and display “normal” chemical shifts in the ¹H NMR spectra. For two of the structurally characterized [(corrolato)­{FeNO}⁶] derivatives, the Fe–N–O bond angles are 175.0(4)° and 171.70(3)° (DFT: 179.94°), respectively, and are designated as linear nitrosyls. The Fe–N (NO) bond distances are 1.656(4) Å and 1.650(3) Å (DFT: 1.597 Å), which point toward a significant Fe^III → NO back bonding. The NO bond lengths are 1.159(5) Å and 1.162(3) Å (DFT: 1.162 Å) and depict their elongated character. These structural data are typical for low-spin Fe­(III). Electrochemical measurements show the presence of a one-electron oxidation and a one-electron reduction process for all the complexes. The one-electron oxidized species of a representative [(corrolato)­{FeNO}⁶] complex exhibits ligand to ligand charge transfer (LLCT) transitions (cor­(π) → cor­(π*)) at 399 and 637 nm, and the one-electron reduced species shows metal to ligand charge transfer (MLCT) transition (Fe­(dπ) → cor­(π*)) in the UV region at 330 nm. The shift of the ν_NO stretching frequency of a representative [(corrolato)­{FeNO}⁶] complex on one-electron oxidation occurs from 1782 cm^–1 to 1820 cm^–1, which corresponds to 38 cm^–1, and on one-electron reduction occurs from 1782 cm^–1 to 1605 cm^–1, which corresponds to 177 cm^–1. The X-band electron paramagnetic resonance (EPR) spectrum of one-electron oxidation at 295 K in CH₂Cl₂/0.1 M Bu₄NPF₆ displays an isotropic signal centered at <i>g</i> = 2.005 with a peak-to-peak separation of about 15 G. The in situ generated one-electron reduced species in CH₂Cl₂/0.1 M Bu₄NPF₆ at 295 K shows an isotropic signal centered at <i>g</i> = 2.029. The 99% contribution of corrole to the HOMO of native species indicates that oxidation occurs from the corrole moiety. The results of the electrochemical and spectroelectrochemical measurements and density functional theory calculations clearly display a preference of the {FeNO}⁶ unit to get reduced during the reduction step and the corrolato unit to get oxidized during the anodic process. Comparisons are presented with the structural, electrochemical, and spectroelectrochemical data of related compounds reported in the literature, with a particular focus on the interpretation of the EPR spectrum of the one-electron oxidized form