Theoretical Approach To the Thermochemistry of Geminal Interactions in Xy(2)h(n) Compounds (x=c, N, O, Si, P, S, Y=nh2,Oh, F, Sih3, Ph2, Sh) - the Generalized Anomeric Effect Reexamined

Leroy, Georges;Dewispelaere, JP.;Benkadour, H.;Temsamani, DR.;Wilante, Claude
(1995) Journal of Molecular Structure: THEOCHEM — Vol. 334, n° 2-3, p. 137-143 (1995)

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Authors
  • Leroy, GeorgesUCLouvain
    Author
  • Dewispelaere, JP.
    Author
  • Benkadour, H.
    Author
  • Temsamani, DR.
    Author
  • Wilante, ClaudeUCLouvain
    Author
Abstract
The enthalpies of formation of a series of XY(2)H(n) compounds have been calculated using the homodesmic reaction XY(2)H(n) + CH(3)XH(n)CH(3) --> 2CH(3)XH(n)Y with total energies computed at the MP2 = FULL/6-31G(d,p)//MP2 = FULL/ 6-31G(d,p) level. The unifying concept of thermodynamic stabilization energy allowed us to estimate the magnitude of the interaction between two substituents attached to a common saturated center. The so-called geminal interaction varies from 9 to -4 kcal mol(-1) in the series of compounds considered in this work. The generalized anomeric effect which is only a part of the geminal interaction cannot be used for rationalizing the thermochemistry of reactions involving XY(2)H(n) compounds.
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Leroy, G., Dewispelaere, JP., Benkadour, H., Temsamani, DR., & Wilante, C. (1995). Theoretical Approach To the Thermochemistry of Geminal Interactions in Xy(2)h(n) Compounds (x=c, N, O, Si, P, S, Y=nh2,Oh, F, Sih3, Ph2, Sh) - the Generalized Anomeric Effect Reexamined. Journal of Molecular Structure: THEOCHEM, 334(2-3), 137-143. https://doi.org/10.1016/0166-1280(94)04034-P (Original work published 1995)