Ab initio molecular dynamics studies on substitution vs electron transfer reactions of substituted ketyl radical anions with chloroalkanes: How do the two products form in a borderline mechanism?

Hiroshi Yamataka, Misako Aida, Michel Dupuis

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20 Citations (Scopus)


We present a qualitative analysis, based on ab initio molecular dynamics (MD) calculations, of the SN2/ ET mechanistic spectrum for three reactions: (1) HC(CN)=O.- + CH3Cl, (2) HC(CN)=O .- + (CH3)2CHCl and (3) H2C=O .- + CH3Cl, passing through their SN2-like transition states. Finite temperature (298 K) direct MD simulations indicate that the trajectories for reaction (1) appear to have a propensity towards SN2 products, the propensity for trajectories for reaction (2) seems to be towards ET products, whereas trajectories for reaction (3) appear to show no particular propensity towards either ET or SN2 products. The mechanistic diversity is consistent with the electron-donating ability of the ketyl species and steric bulkiness of chloroalkanes. We find that the trajectories have characteristics that reflect strongly the types of process [SN2 trajectories in reactions (1) and (3) vs ET trajectories in reactions (2) and (3)]. Trajectories that lead to SN2 products are simple with C-C bond formation and C-Cl bond breaking essentially completed within 50 fs. By contrast, trajectories leading to ET products are more complex with a sudden electron reorganization taking place within 15-30 fs and the major bonding changes and electron and spin reorganizations completed after 250 fs.

Original languageEnglish
Pages (from-to)475-483
Number of pages9
JournalJournal of Physical Organic Chemistry
Issue number8
Publication statusPublished - Aug 1 2003



  • Borderline mechanism
  • Direct molecular dynamics simulation
  • Electron transfer
  • MO calculations
  • S2
  • Transition state

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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