Regular Article

Theoretical Chemistry Accounts

, Volume 119, Issue 5, pp 453-462

First online:

A theoretical study of thermodynamics and kinetics of nitrosamines: a potential no carrier

  • Chin-Hung LaiAffiliated withDepartment of Chemistry, National Taiwan University Email author 
  • , Pi-Tai ChouAffiliated withDepartment of Chemistry, National Taiwan University

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In this theoretical study, several hybird DFT functionals and MP2 method are used to investigate the properties and the kinetics of a series of nitrosamines. The results show SN or NS transnitrosation reaction to be more favorable via an SN2-like pathway. The stability is predicted to be in the order of H2NNO > cis-MeHNNO > trans-MeHNNO > Me2NNO > trans-PhHNNO > cis-PhHNNO > cis-MeSNO > Ph2NNO > N-methylenenitrous amide, in which Ph2NNO and N-methylenenitrous amide will be potential candidates for the NO donor. For N-methylenenitrous amide, which has the strongest NO donating strength among the titled nitroamines, a nearly perpendicular configuration between H2C=N and NO can plausibly be rationalized by the fact that lone pair of the nitrogen atom on the fragment H2CN must be π-type, not σ-type, to form a mesomeric effect with π*N-O of the NO group. Using the polarizable continuum model to consider the water solvent effect, all the barriers and endothermicities of the transnitrosation reactions are decreased and the correlated %N–H and %N–S are decreased and increased.


DFT Nitrosamines SN transnitrosation reaction Mesomeric effect