Possible structures for trimethylene radical cations in freon matrices
1985; Elsevier BV; Volume: 117; Issue: 4 Linguagem: Inglês
10.1016/0009-2614(85)85248-9
ISSN1873-4448
Autores Tópico(s)Photochemistry and Electron Transfer Studies
ResumoIt has recently been shown that the parent, cyclic structure for the cyclopropane radical cation undergoes ring opening in a CFCl2CF2Cl matrix. However, the ESR results show that the derived species has a SOMO localised on only one of the terminal CH2 groups. This apparently requires a limiting orthogonal structure for the outer CH2 groups rendering one similar to a normal alkyl radical and the other to a normal carbocation. Since CH hyperconjugation for the CH2+ unit is minimised by the structure detected, it will be an extremely powerful electrophile. It is therefore suggested that bonding to one chlorine ligand of a solvent molecule occurs. However, if this is the species studied by ESR spectroscopy, there is no need to postulate that the uncomplexed cation has an orthogonal ground state, since the solvent adduct could have been formed from the linear radical cation in any conformation.
Referência(s)