Abstract
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.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
P.J. Krueger, Can. J. Chem., 40. 2300 (1962).
H.H. Jaffe, J. Am. Chem. Soc., 79. 2373 (1957).
P. von R. Schleyer and R. West, J. Am. Chem. Soc., 81, 3164 (1959).
R. West, D. L. Powell, L. S. Whatley, M. K. T. Lee J. Am. Chem. Soc., 84. 3221 (1962).
P.J. Krueger and H.D. Mettee, Can. J. Chem., 42, 326 (1964).
O.R. Wulf, V. Liddel, and S.B. Hendricks, J. Am. Chem. Soc., 58, 2287 (1936).
L. Pauling, J. Am. Chem. Soc.. 58, 94 (1936).
A. W. Baker and W. W. Kaeding, J. Am. Chem. Soc., 81, 5904 (1959).
H. Bourassa-Bataille, P. Sauvageau, and C. Sandorfy. Can J. Chem.. 41. 2240 (1963).
E.A. Allan and L. W. Reeves, J. Phys. Chem., 67, 591 (1963).
A.G. Moritz, Spectrochim. Acta, 16, 1176 (1960).
A.G. Moritz, Spectrochim. Acta, 18, 671 (1962).
G.D. Bagratishvili, G. V. Tsitsishvili, and K.A. Bezhashvili, Zhur. Fiz. Khim., 36, 2036 (1962).
A. N. Hambly and B. V. O#x2019;Grady, Chem. and Ind. (London) 15. 459 (1962).
A. N. Hambly and B. V. O#x2019;Grady, Australian J. Chem., 15. 626 (1962).
P.J. Krueger, AppL Opt.. 1. 443 (1962).
S. Califano and R. Moccia. Gazz. chim. ital.. 87. 805 (1957).
P.J. Krueger. Can. J. Chem., 42, 201 (1964).
R.A. Nyquist, Spectrochim. Acta. 19, 1595 (1963).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1965 Chicago Section of the Society for Applied Spectroscopy
About this paper
Cite this paper
Krueger, P.J., Smith, D.W. (1965). Intramolecular NH ••• Halogen Hydrogen-Bond Strengths in Five- and Six-Membered Chelate Rings. In: Davis, E.N. (eds) Developments in Applied Spectroscopy. Developments in Applied Spectroscopy, vol 4. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-8691-9_17
Download citation
DOI: https://doi.org/10.1007/978-1-4684-8691-9_17
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4684-8693-3
Online ISBN: 978-1-4684-8691-9
eBook Packages: Springer Book Archive