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The Stability of α‐Hydroperoxyalkyl Radicals
Author(s) -
Anglada Josep M.,
Crehuet Ramon,
Francisco Joseph S.
Publication year - 2016
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.201604499
Subject(s) - radical , chemistry , unpaired electron , steric effects , bond dissociation energy , dissociation (chemistry) , computational chemistry , decomposition , photochemistry , stereochemistry , organic chemistry
High‐level ab initio and Born–Oppenheimer molecular dynamic calculations have been carried out on a series of hydroperoxyalkyl (α‐QOOH) radicals with the aim of investigating the stability and unimolecular decomposition mechanism into QO+OH of these species. Dissociation was shown to take place through rotation of the C−O(OH) bond rather than through elongation of the CO−OH bond. Through the C−O(OH) rotation, the unpaired electron of the radical overlaps with the electron density on the O−OH bond, and from this overlap the C=O π bond forms and the O−OH bond breaks spontaneously. The CH 2 OOH, CH(CH 3 )OOH, CH(OH)OOH, and α‐hydroperoxycycloheptadienyl radical were found to decompose spontaneously, but the CH(CHO)OOH has a decomposition energy barrier of 5.95 kcal mol −1 owing to its steric and electronic features. The systems studied in this work provide the first insights into how structural and electronic effects govern the stabilizing influence on elusive α‐QOOH radicals.