Stereoelectronic effects of porphyrin ligand on the oxygen transfer efficiency of high valent manganese-oxo porphyrin species: A DFT study

Abstract

The structure and properties of the N[Formula: see text]–Mn–O bonds of high valent manganese-oxo of the second and third generation porphyrins in the presence of imidazole have been studied by means of density functional (DFT) method with 6-31G* basis set in the gas phase as well as water solution. The geometric structures, frontier molecular orbitals, thermodynamic parameters, aromaticity indices and physical properties such as chemical potential and chemical hardness of [(TPP)(ImH)MnO][Formula: see text] and its derivatives were calculated. The obtained results showed that [(TPP)(ImH)MnO][Formula: see text] bearing halogen atoms at the [Formula: see text]-pyrrole positions had a saddle conformation with low Mn–O strength. The electron density ([Formula: see text] and Laplacian ([Formula: see text] properties at critical points of the N[Formula: see text]–Mn–O bonds, estimated by AIM calculations, indicate that Mn–O bonds in third generation porphyrins have lower [Formula: see text] and Mn–N[Formula: see text] distances have higher [Formula: see text] than the second generation ones. The calculations of aromaticity indices for chelated rings at the porphyrin center show that HOMA and NICS in third generation porphyrins are generally lower than that of second ones which is in agreement with their saddle conformation. These results are supported by natural bond orbital (NBO) analysis.