Mechanism of the uncatalysed syn–anti-isomerization of imine systems. Part IV. A theoretical study of the influence of substituents
- 1 January 1971
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society B: Physical Organic
- p. 541-544
- https://doi.org/10.1039/j29710000541
Abstract
Extended Hückel (Hoffmann) calculations have been performed for the ‘lateral shift’syn–anti-isomerization of seven simple imine derivatives H2CN–X (X = H, Me, NH2, OH, F, Cl, and Br). The energy-barrier values obtained are in satisfactory agreement with the experimental data (except those for X = Cl or Br). The computed ‘reduced overlap population’ for the N–X bond, and the ‘gross atomic population’ values for the nitrogen atom, together with previous data show that our hypothesis about the influence of the N-bonded substituent is valid: i.e., the isomerization energy barrier isgreatest for substituents with a strong –l(inductive) but no –M(mesomeric) effect.Keywords
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