Stereoelectronic Effects and General Trends in Hyperconjugative Acceptor Ability of σ Bonds

Abstract

A systematic study of general trends in sigma acceptor properties of C-X bonds where X is a main group element from groups IVa-IIa is presented. The acceptor ability of the C-X sigma bonds in monosubstituted ethanes increases when going to the end of a period and down a group. Enhancement of acceptor ability of C-X sigma bonds as one moves from left to right in periods parallels the increase in electronegativity of X, whereas augmentation of acceptor ability in groups is opposite to the changes in electronegativity of X and in the C-X bond polarization, following instead the decrease in the energy of sigma(C)(-)(X) orbitals when one moves from the top to the bottom within a group. This simple picture of acceptor ability of sigma bonds being controlled by electronegativity in periods and by sigma orbital energy in groups is changed in monosubstituted ethenes where the role of electronegativity of the substituent X becomes more important due to increased overlap between sigma orbitals. The combination of several effects of similar magnitude influences acceptor ability of sigma bonds in monosubstituted ethenes in a complex way. As a result, the acceptor ability of sigma bonds can be significantly modified by substitution and is conformer dependent. Stereoelectronic effects displayed by C-X bonds with X from second and third periods are highly anisotropic. For example, C-chalcogen bonds are excellent sigma acceptors at the carbon end but poor sigma acceptors at the chalcogen end. This effect can be relied upon in the design of molecular diodes with sigma bridges with unidirectional electron conductivity. While the general trends revealed in this work should be useful for the qualitative understanding of stereoelectronic effects, one should bear in mind that the magnitude of hyperconjugative effects is extremely sensitive to small variations in structure and in substitution. This advocates for the increased role of theoretical methods in analysis of stereoelectronic effects.

Estabilidade relativa de alcenos: análise dos critérios encontrados nos livros textos de graduação e uma proposta de explicação operacional para alcenos dissubstituídos

“…Em carbocátions e em estados excitados, a hiperconjugação é um fator significativo para a estabilização, mas a sua contribuição na estabilidade de moléculas neutras no estado fundamental é matéria de debate. Porém, recentemente, provas experimentais tais como valores de constantes de acoplamento, barreiras rotacionais e calores de reação têm fortalecido o seu emprego 14,15 . O fenômeno de hiperconjugação em moléculas neutras no estado fundamental pode ser invocado como sendo o fator responsável por pequenas diferenças de energia de moléculas de alcenos isoméricos, como os do Esquema 1.…”

4‐Chloroprolines: Synthesis, conformational analysis, and effect on the collagen triple helix

“…50 The stereoelectronic effect that controls proline ring pucker can be regarded as a hyperconjugative effect, 35 and Shoulders, Guzei, and Raines page 6 natural bond order analysis suggests that σ* C-Cl orbitals have a greater acceptor ability than do the corresponding σ* C-F orbitals. 51 Nevertheless, proline ring pucker is controlled by competing stereoelectronic and steric effects, 31,35 and chlorine has a significantly larger covalent radius than does fluorine (r F = 0.64 Å; r Cl = 0.77 Å). Hence, it was not apparent a priori whether the electronegativity or the size of a 4-chloro substitution would dominate its effect on proline ring pucker.…”

Conformational Preference of 4-Ethyl- 6-Methyl-1,3-Dithianes

“…2 stands for the population of the donor orbital. There is good linear correlation between the second-order perturbation hyperconjugative energies and the deletion procedure 23 .…”