Reevaluation of orbital interactions in substituted radicals. Transfer of radical properties to the substituent atom

✍ Scribed by Daniel J. Pasto

• Book ID: 104218767
• Publisher: Elsevier Science
• Year: 1986
• Tongue: French
• Weight: 184 KB
• Volume: 27
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)84685-7

✦ Synopsis

Theoretical calculations have shown that a nonbonded pair orbital on an atom attached to a radical center can be higher in energy than the SOMO of the unsubstituted radical. The mixing of the orbitals produces a SOMO which contains the major contribution from the nonbonded pair orbital, thus transferring radical character to the substituent atom. Recent studies in several laboratories have focused on the effects of various substituents on the rates of radical reactionslm4 and on the delocalization of spin density.5 The interactions of a radical center with adjacent bonding and nonbonding pairs of electrons have been qualitatively analyzed using PM0 theory, the interactions being illustrated in the energy diagrams in Fig. 1.6 From a quantitative viewpoint there are serious errors in