A theoretical approach to the thermochemistry of the isomerization reactions CH2XCHYCH3 double left right arrow CH2YCHXCH3 (X = OH, Y = PH2, CH3, SH, NH2, Cl, X = Cl, Y = PH2, SH, NH2, X = NH2, Y = PH2, SH, X = SH, Y = PH2)

Leroy, Georges;Dewispelaere, JP.;Wilante, Claude
(1998) Journal of Molecular Structure: THEOCHEM — Vol. 433, p. 239-245 (1998)

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Authors
  • Leroy, GeorgesUCLouvain
    Author
  • Dewispelaere, JP.
    Author
  • Wilante, ClaudeUCLouvain
    Author
Abstract
The thermodynamic parameters of the isomerization reactions CH2XCHYCH3 = CH2YCHXCH3 have been calculated at the HF/6-31G (d,p)//HF 6-31G (d,p) level using the usual formalism of statistical thermodynamics. The enthalpies of isomerization have been further rationalized in terms of the variations of the sums of the bond energy terms and the stabilization energies of both isomers. We have shown that the heats of isomerization are roughly proportional to the difference between the electronegativities of the heavy atoms of the substitutents X and Y:Delta H-0(0), = k(x(Y) - x(x)) (k >0). Therefore, the considered isomerization reactions are expected to be exothermic when xx is larger than xy which is systematically verified as much theoretically as experimentally. (C) 1998 Elsevier Science B.V. All rights reserved.
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Leroy, G., Dewispelaere, JP., & Wilante, C. (1998). A theoretical approach to the thermochemistry of the isomerization reactions CH2XCHYCH3 double left right arrow CH2YCHXCH3 (X = OH, Y = PH2, CH3, SH, NH2, Cl, X = Cl, Y = PH2, SH, NH2, X = NH2, Y = PH2, SH, X = SH, Y = PH2). Journal of Molecular Structure: THEOCHEM, 433, 239-245. https://doi.org/10.1016/S0166-1280(98)00030-X (Original work published 1998)