Mechanistic insights into intramolecular ortho-amination/hydroxylation by nonheme FeIV[double bond, length as m-dash]NTs/FeIV[double bond, length as m-dash]O species: the σ vs. the π channels.

Comparative oxidative abilities of nonheme FeIV[double bond, length as m-dash]NTs and FeIV[double bond, length as m-dash]O species using DFT has been explored. Our calculations reveal that the FeIV[double bond, length as m-dash]NTs is found to be a stronger oxidant in two electron transfer reactions and react exclusively via π channels while the FeIV[double bond, length as m-dash]O species is found to be a stronger oxidant when the σ-pathway is activated such as in HAT reactions.