Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A Quantitative Analysis of $\pi$-Nobonded and Through-Bond Interactions in n-Butane, n-Buthyl Radical and Tetramethylene Diradical$^1$

  • Published : 1982.03.31
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Abstract

A quantitative treatment of ${\pi}$-nonbonded and $n-{\sigma}^{\ast}$ interactions and through-bond coupling effect was attempted using n-butane, n-butyl radical, and tetramethylene diradical. Results of STO-3G level calculations showed that: (1) conformational preferences can be predicted quantitatively based solely on the additive effect of ${\pi}$-nonbonded and $n-{\sigma}^{\ast}$ interactions, the predominant effect being the ${\pi}$-nonbonded interactions, (2) $(n-{\sigma}^{\ast})_{anti}$ is destabilizing whereas $(n-{\sigma}^{\ast})_{syn}$ is weakly stabilizing, which are contrary to what we expect from the normal $n-{\sigma}^{\ast}$ interaction, (3) througb-bond coupling of the two radical lobes is destabilizing for the triplet but stabilizing for the singlet tetramethylene diradical.

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  1. Theoretical studies on the reaction of phosphoranes with anions vol.279, pp.None, 1982, https://doi.org/10.1016/0166-1280(93)90066-k