A MO Study of β‐Substituted Ethyl Radicals

Tova Hoz, Milon Sprecher, Harold Basch

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The preferred ground state conformation of β‐substituted ethyl radicals, with the Cβ heteroatom substituent group being PH2, SH and CI1 have been determined by ab initio spin‐unrestricted self‐consistent field gradient optimization techniques. All the ground state geometries are found to have the Cβ‐heteroatom bond coplanar with the Cα‐centered radical orbital. No tendency towards heteroatom group bridging between Cα and Cβ is found in the systems studied here. The radical centers are calculated to be non‐planar, with the Cα hydrogen atoms tilting towards the Cβ substituent group. Calculated rotation energy profiles about the Cα‐Cβ and Cβ‐heteroatoms bonds, as well as the atomic orbital spin population distributions, are interpreted in terms of possible interactions between the Cα‐centered radical orbital and the Cβ‐heteroatom σ bond orbitals (hyperconjugation, type I) or the heteroatom 3d (type II) or lone pair (type III) atomic orbitals. Type I is the only significant stabilizing interaction found in these systems, whereas the type III (two orbital, three electron) interaction is actually found to be destabilizing.

Original languageEnglish
Pages (from-to)109-115
Number of pages7
JournalIsrael Journal of Chemistry
Issue number1
StatePublished - 1983


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