A mechanistic study of the manganese porphyrin-catalyzed C–H isocyanation reaction

The favourable radical rebound pathway is NCO-rebound from the Mn(TMP)(NCO)2 complex due to the stronger trans effect of the axial ligand NCO and the electron-donating aryl substituents on the porphyrin ligand.

The Simplest Iron μ-oxo Species. The Molecular Structure of {[Fe(porphine)]2O}

We have prepared a new [Formula: see text]-oxo iron(III) porphyrin complex based on the simplest possible porphyrin ligand, porphine. Our structure determination for {[Fe(porphine)]2O}shows that it has a decidedly different molecular structure compared to all other [Formula: see text]-oxo iron(III)porphyrin complexes with two independent porphyrin ligands. The Fe–O–Fe angle is 153.21 (16)[Formula: see text]which leads to a small interplanar angle of 22.7[Formula: see text]between the two porphine rings. This also leads to C[Formula: see text]C nonbonded contact as short as 3.35Å between the two rings. The twist angle of the two porphine rings is 16.8[Formula: see text]. Other structural features are in general accord with those expected for high-spin iron(III) porphyrinates.