Intramolecular NH ••• Halogen Hydrogen-Bond Strengths in Five- and Six-Membered Chelate Rings

  • P. J. Krueger
  • D. W. Smith
Part of the Developments in Applied Spectroscopy book series (DAIS, volume 4)


The fundamental symmetric and asymmetric NH2, NHD, and ND2 stretching vibrations are compared in o- and p-haloanilines, -benzylamines, and -benzamides in dilute solution. Ortho-substituted benzylamines exhibit rotational isomerism, with free NH2 groups and intramolecularIv-bonded NH2 groups. The cis—trans isomerism of the NHD group in mono-deuterated-o-haloanilines and o-benzamides indicates that the intramolecular NH··· X hydrogen-bond strength increases in the former in the order X = F < CI < Br < I, but that the reverse order holds for the latter (as well as for o-halobenzylamines). These results are discussed in terms of the halogen size, the halogen electronegativity, and the geometry of the chelate system. In mono-deutero-o-haloanilines, ND···X bonds appear to be weaker than NH···X bonds.


Halogen Atom Chelate Ring Rotational Isomerism Relative Frequency Shift Frequency Displacement 
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Copyright information

© Chicago Section of the Society for Applied Spectroscopy 1965

Authors and Affiliations

  • P. J. Krueger
    • 1
  • D. W. Smith
    • 1
  1. 1.University of AlbertaCalgaryCanada

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