A theoretical study of thermodynamics and kinetics of nitrosamines: A potential no carrier
Resource
Theoretical Chemistry Accounts: Theory, Computation, and Modeling 119 (5-6): 453-462
Journal
Theoretical Chemistry Accounts
Journal Volume
119
Journal Issue
5-6
Pages
453-462
Date Issued
2008
Author(s)
Lai, C.-H.
Abstract
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 > Me 2NNO > trans-PhHNNO > cis-PhHNNO > cis-MeSNO > Ph 2NNO > 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 H 2C=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. © 2007 Springer-Verlag.
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