• Journal of the Korean Chemical Society
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• v.17 no.2
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• pp.95-104
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• 1973

Ground electronic structures and SNreactivities of a series of alkylchlorides (methyl,ethyl, iso-propyl, trans n-butyl, sec-butyl, tert-butylchloride) have been studied using approximate $({\sigma}-MO)$ method, such as EHT and CNDO/2. It was found that CNDO/2 gives better results for the systems such as alkylchlorides whose structural differences are not remarkable, in comparison with EHT method. According to CNDO/2 results, calculated dipole moments for alkylchlorides are slightly higher than observed values, showing the order of primary < secondary < tertiary alkylchlorides. It was also found that highest occupied(HO) MO's are completely or nearly degenerate, and show relatively weak $\pi$-antibonding nature between$\alpha$-carbon and Cl atoms. Furthermore, the electrons in this MO are largely confined to Cl atom, and hence these behaves as likely as p-lone pair electrons of Cl atom. On the contrary, lowest unoccupied (LU) MO's show strong $\sigma$-antibonding nature between $\alpha$-carbon and Cl atoms whose electron clouds are directed along the C-Cl axis. It has been discussed that the$S_N2$ reactivities of alkylchlorides may largely be controlled by ${\sigma}^{\ast}$ LUMO, and the antibonding strength between $\alpha$-carbon and Cl atoms in this MO may become the measure of $S_N2$reactivity. The relationship between $S_N2$reactivity and C-Cl bond polarizability has also been discussed. It has been suggested that the unique structure factors determining $S_N1$reactivities may be $\pi$-antibonding strength between $\alpha$-carbon and Cl atoms in HOMO and C-Cl bond strength in ground state.