The Decisive Role for Secondary Coordination Sphere Nucleophiles on Hydrogen Atom Transfer (HAT) Reactions: Does It Exist and What Is Its Origin?

Abstract

Although it has been reported that some radical reactions are possibly promoted by external ions, the origin of this phenomenon is unclear. In this work, several hydrogen atom transfer (HAT) reactions in the presence of anions were studied by density functional theory (DFT) calculations, electronic structure analysis and other methods, and it is concluded that both the electrostatic interaction and polarization of the transition state (TS) by the electric field generated by anions play a fundamental role in the TS stabilization effect, whereas the “charge shift bonding” that was previously presumed to be a major contributor is ruled out. Although the stabilization toward TSs in terms of electronic energy (and thus enthalpy) is significant, it should be noted that the effect is almost completely cancelled by entropy and solvation, and further cancelled by the formation of stable resting states. Thus there is still a long way for this effect to be used in actual catalysis.