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A theoretical study of α-substituted cyclopropyl and isopropyl radicals

✍ Scribed by M. H. Lien; A. C. Hopkinson

Publisher
John Wiley and Sons
Year
1985
Tongue
English
Weight
692 KB
Volume
6
Category
Article
ISSN
0192-8651

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✦ Synopsis

The structures of a-X-cyclopropyl and a-X-isopropyl radicals (X = H, CH3, NH2, OH, F, CN, and NC) are reported at the RHF 3-21G level of theory. The isopropyl radicals are pyramidal with out-of-plane angles varying from 12" (X = CN) to 39" (X = NH2), and barriers to inversion ranging from 0.4 kcal/mol (X = H) to 4.0 kcal/mol (X = NH2). The cyclopropyl radicals have larger out-of-plane angles, from 39.9" (X = CN) to 49.4" (X = NHa), and their barriers to inversion, which increase with the inclusion of polarization functions, vary from 5.5 kcal/mol (X = H) to 16.7 kcal/mol (X = F). In both types of radicals the amino group is the most stabilizing substituent, while the a-fluoro has little effect. The p-fluoro group is weakly destabilizing in the cyclopropyl radical. The strain energies of the cyclopropyl radicals (36-43 kcal/mol) are compared with those of similarly substituted anions, cations, and cyclopropanes.

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