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Mechanism of the Hydrogen Transfer from the OH Group to Oxygen‐Centered Radicals: Proton‐Coupled Electron‐Transfer versus Radical Hydrogen Abstraction
Author(s) -
Olivella Santiago,
Anglada Josep M.,
Solé Albert,
Bofill Josep M.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305714
Subject(s) - chemistry , hydrogen atom abstraction , hydrogen atom , electron transfer , radical , proton coupled electron transfer , intramolecular force , proton , hydrogen , unpaired electron , intermolecular force , photochemistry , molecule , chemical physics , computational chemistry , stereochemistry , organic chemistry , physics , alkyl , quantum mechanics
High‐level ab initio electronic structure calculations have been carried out with respect to the intermolecular hydrogen‐transfer reaction HCOOH+ . OH→HCOO . +H 2 O and the intramolecular hydrogen‐transfer reaction . OOCH 2 OH→HOOCH 2 O . . 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 topological 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 proton‐coupled 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.