Abstract
IT has previously been suggested1 that the energy of a bond is related to the overlap integral of the two atomic orbitals which are thought to form the bond. To try to provide a quantitative expression of this idea we have assumed that the bond energy is directly proportional to the overlap integral of the bond orbitals. The proportionality constant can be evaluated by using the bond energy of the CSp 3 – CSp 3 single bond obtained from experimental values of the heats of formation of saturated long-chain hydrocarbons2. The bond energies of the five other types of carbon–carbon single bonds may then be calculated by using tables of overlap integrals3 and the appropriate bond lengths4 (Table 1). Then by using the Csp 2–H bond energy, obtained from the same set of data as the tetrahedral carbon–carbon bond energy, and the observed2 heats of formation of ethylene, propylene, acetylene and propyne, the bond energies for the carbon–carbon double and triple bonds and the Csp 2H and CSp–H. bonds can be calculated (Table 1). This table of ‘standard’ bond energies can then be used to predict the heats of formation and heats of hydrogenation of any unsaturated hydrocarbon for which steric effects are small (Table 2). It is seen that the predicted values are quite close to the experimental ones even in cases where there is usually considered to be considerable resonance or hyperconjungative stabilization; in fact, most of the results show a small destabilization energy probably due to the simplifying assumption of neglecting polar effects and non-bonding interactions.
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BLOOR, J., GARTSIDE, S. Effect of Hybridization Changes on the Bond Energies of Carbon–Carbon Single Bonds. Nature 184, 1313 (1959). https://doi.org/10.1038/1841313a0
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DOI: https://doi.org/10.1038/1841313a0
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