The Interaction of Dihalogens and Hydrogen Halides with Lewis Bases in the Gas Phase: An Experimental Comparison of the Halogen Bond and the Hydrogen Bond - Halogen Bonding: Fundamentals and Applications - page 58

There are other parallels between the series of complexes B ··· XY and

B HX have, in general,

similar binding strengths, as measured by the intermolecular stretching force
constant k σ ,andbothare,forthemostpart,weaklybound.Wehavealsoshown
in Sect. 5 that the electric charge redistribution that occurs when B

··· HX. We established in Sect. 4 that B ··· XY and B ···

XY is
formed from its components B and XY is generally small (exceptions among
both halogen- and hydrogen-bonded complexes were discussed).
The striking parallel behaviour among the various properties of B

···

··· XY

and B HX suggests that the origin of the halogen-bond interaction might be

similar to that of the hydrogen bond interaction. An electrostatic model has
had much success in predicting angular geometries, both qualitatively [103,
104] and quantitatively [206]. In first approximation, an electrostatic model is
one which takes into account only the interaction of the unperturbed electric
charge distributions of the two component molecules as they come together
to form the complex in its equilibrium conformation, with contributions from
interactions of any induced moments assumed minor. The empirical rules
set out in Sect. 3 and this section for hydrogen-bonded and halogen-bonded
complexes, respectively, are inherently electrostatic in origin. The reason why
the electrostatic component of the energy is definitive of the angular geom-
etry has been investigated in detail through ab initio calculations [207] for
H 2 O

···

HF. The systematic behaviour of the intermolecular force constants k σ
of hydrogen-bonded complexes has been discussed in terms of a predomin-
antly electrostatic interpretation [181].

···

References

1. Guthrie F (1863) J Chem Soc 16:239
2. Benesi HA, Hildebrand JH (1949) J Am Chem Soc 71:2703
3. Mulliken RS, Person WB (1969) Molecular complexes: A lecture and reprint volume.
Wiley-Interscience, New York
4. Hassel O, Rømming C (1962) Quart Rev Chem Soc 16:1
5. Hassel O (1970) Science 170:497
6. Frei H, Pimentel GC (1985) Annu Rev Phys Chem 36:491
7. Bai H, Ault BS (1990) J Phys Chem 94:199
8. Bai H, Ault BS (1990) J Mol Struct 238:223
9. Machara NP, Ault BS (1988) J Mol Struct 172:126
10. Machara NP, Ault BS (1988) Inorg Chem 27:2383
11. Andrews L, Hunt RD (1988) J Chem Phys 89:3502
12. Andrews L, Lascola R (1987) J Am Chem Soc 109:6243
13. Andrews L, McInnis TC, Hannachi Y (1992) J Phys Chem 96:4248
14. McInnis TC, Andrews L (1992) J Phys Chem 96:2051
15. Legon AC, Rego CA (1990) J Chem Soc Faraday Trans 86:1915
16. Balle TJ, Flygare WH (1981) Ann Rev Sci Instrum 52:33
17. Legon AC (1992) In: Scoles G (ed) Atomic and molecular beam methods, vol 2.
Oxford University Press, New York, p 289