Disproportionation of Iron(III) Porphyrin pi-Cation Radicals in the Presence of Sterically Hindered Pyridines. Spectroscopic Detection of Asymmetric Highly Oxidized Intermediates

The reactivity of iron(III) tetraphenylporphyrin pi-cation radical (TPP(*))Fe(III)(ClO(4))(2), (1-1) iron(III) tetra-p-tolylporphyrin pi-cation radical (TTP(*))Fe(III)(ClO(4))(2) (1-2) and iron(III) tetramesitylporphyrin pi-cation radical (TMP(*))Fe(III)(ClO(4))(2) (1-3) complexes with 2,4,6-collidine, 2,3,6-collidine, 2-picoline, 2,6-di-tert-butylpyridine, and 2,6-dibromopyridine has been examined by (1)H NMR spectroscopy in dichloromethane-d(2) solution at low temperatures. These complexes undergo hydration processes which are essential in the generation of highly oxidized species via acid base/equilibria of coordinated water followed by disproportionation pathway, giving as sole stable products (TPP(*))Fe(III)OFe(III)(TPP)](+) (4-1), (TTP(*))Fe(III)OFe(III)(TTP)](+) (4-2), and (TMP)Fe(III)(OH) (6) respectively. The sterically hindered pyridines act as efficient proton scavengers. Two novel highly oxidized iron complexes have been detected by (1)H NMR spectroscopy after addition of 2,4,6-collidine to (TTP(*))Fe(III)(ClO(4))(2) or (TPP(*))Fe(III)(ClO(4))(2) in dichloromethane-d(2) solution at 202 K. New intermediates have been identified as iron porphyrin N-oxide complexes, i.e., iron(III) porphyrin N-oxide cation radical (2-n) and iron(IV) porphyrin N-oxide radical (3-n). The (1)H NMR results indicate that the D(4)(h)() symmetry of the parent iron(III) pi-cation radical is drastically reduced upon disproportionation in the presence of proton scavengers. Both species are very unstable and were observed from 176 to 232 K. The intermediate 2-2 has a (1)H NMR spectrum which demonstrates large hyperfine shifts (ppm) for the meso p-tolyl substituents (ortho 98.0, 94.8, 92.9, 91.7; meta -34.8, -38.7, -41.5, -42.3; p-CH(3) -86.3, -88.0) which are consistent with presence of an N-substituted iron porphyrin radical in the product mixture. The characteristic (1)H NMR spectrum of 2-2 includes six pyrrole resonances at 149.6, 118.2, 115.4, 88.3, 64.6, and 55.7 ppm at 202 K, i.e., in the positions corresponding to iron(III) high-spin porphyrins. On warming to 222 K, the pyrrole resonances broaden and then coalesce pairwaise. Such dynamic behavior is accounted for by a rearrangement mechanism which involves an inversion of the porphyrin puckering. The pattern of p-tolyl resonances revealed the cation radical electronic structure of 3-2. The p-tolyl resonances are divided in two distinct sets showing opposite direction of the isotropic shift for the same ring positions. The pyrrole resonances of 3-2 also demonstrated downfield and upfield shifts. A disproportionation mechanism of the hydrated iron porphyrin cation radicals to generate 2 and 3 has been proposed. Both intermediates react with triphenylphosphine to produce triphenylphosphine oxide and high-spin iron porphyrins. Addition of 2,4,6-collidine to (TMP(*))Fe(III)(ClO(4))(2) does not produce analogs of 2 and 3 found for sterically unprotected porphyrins. It results instead in the formation of a variety of X(TMP(*))Fe(IV)O (5) complexes also accounted for by the disproportionation process.