Mechanism of the Hydrogen Transfer from the OH Group to Oxygen-Centered Radicals:Proton-Coupled Electron-Transfer versus Radical Hydrogen Abstraction

摘要

High-level ab initio electronic structure calculations have been carried out with respect to the inter-molecular hydrogen-transfer reaction HCOOH+~·OH->HCOO~+H_2O and the intramolecular hydrogen-transfer reaction ~oOOCH_2OH->HOOCH_2O~·.In both cases we found that the hydrogen atom transfer can take place via two different transition structures.The lowest energy transition structure involves a proton transfer coupled to an electron transfer from the ROH species to the radical,whereas the higher energy transition structure corresponds to the conventional radical hydrogen atom abstraction.An analysis of the atomic spin population,computed within the framework of the topologi-cal theory of atoms in molecules,suggests that the triplet repulsion between the unpaired electrons located on the oxygen atoms that undergo hydrogen exchange must be much higher in the transition structure for the radical hydrogen abstraction than that for the protoncoupled electron-transfer mechanism.It is suggested that,in the gas phase,hydrogen atom transfer from the OH group to oxygen-centered radicals occurs by the proton-coupled electron-transfer mechanism when this pathway is accessible.