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The strength and length of donor-acceptor bonds in molecular complexes

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Abstract

Numerous published data on the structure and thermodynamics of formation of molecular complexes are analyzed. The enthalpies of complexation (−ΔH) are related to the characteristic parameter Δr = [r DA−a 1(r D+r A)], where r DA is the donor-acceptor bond length determined by microwave spectroscopy and X-ray analysis, r D and r A are the tabulated values of the homopolar covalent radii of the heteroatoms that form the donor-acceptor bond, and a 1 is an empirical coefficient equal to 0.901±0.007. The relation between −ΔH and Δr values has the form −ΔH = a 2/Δr (a 2 = 21.6±1.6 kJ Å mol−1), with a mean relative error of approximation of about 15% and a correlation coefficient of 0.97. As the strength of the complex increases, the donor-acceptor bond length approaches the sum of the heteropolar covalent radii of the atoms involved in the bond (Δr tends to zero). At Δr ≫ 1, the strength of complexes is determined by weak van der Waals interactions between the complex components and the −ΔH values tend to zero.

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  1. L. Ya. Karpov Research Physicochemical Institute, 10 ul. Vorontsovo Pole, Moscow, 105064, Russian Federation

    I. P. Romm & A. A. Malkov

  2. Joint Research and Development Center, 55/1, Bldg. 2, Leninskiy Prosp., Moscow, 119333, Russian Federation

    Yu. G. Noskov

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Dedicated to the memory of E. N. Guryanova (1911–2004), a prominent scientist who formulated the basic principles elaborated by her disciples in this review.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1869–1878, October, 2007.

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Romm, I.P., Noskov, Y.G. & Malkov, A.A. The strength and length of donor-acceptor bonds in molecular complexes. Russ Chem Bull 56, 1935–1944 (2007). https://doi.org/10.1007/s11172-007-0300-0

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