A Frontier Orbital Study with Ab Initio Molecular Dynamics of the Effects of Solvation on Chemical Reactivity: Solvent-Induced Orbital Control in FeO-Activated Hydroxylation Reactions

Solvation effects on chemical reactivity are often rationalized using electrostatic considerations: the reduced stabilization of the transition state results in higher reaction barriers and lower reactivity in solution. We demonstrate that the effect of solvation on the relative energies of the frontier orbitals is equally important and may even reverse the trend expected from purely electrostatic arguments. We consider the H abstraction reaction from methane by quintet [EDTAH