The effect of electron-withdrawing groups in the fragmentation of the radical anions of benzyl phenyl ethers

Abstract

a b s t r a c tThe objective of this paper is to compare the influence of two electron-withdrawing groups in the fragmentation of 2-methoxy-4-nitrophenyl benzyl ether and 4-cyanophenyl benzyl ether once these species are reduced. The stability of the corresponding radical anions depends essentially on those substituents. In our design we have chosen two species that are able to attach the electron but which have each a different capacity to retain it. An experimental study is carried out by EPR spectroscopy to analyze the different electronic nature of the generated radical anions. In addition, electronic structure calculations at the DFT level of theory have been performed to study those radical anions and their fragmentation pathways. The thermodynamics and kinetics of the two fragmentations are discussed and compared in detail.

Photoelectron spectroscopy and thermochemistry of o-, m-, and p-methylenephenoxide anions

“…Studies of distonic radical ions, ions that have their radical site separated from their charge site, are also of interest to the scientific community. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Radical ions may react either as radicals or as ions, with their multifunctionality allowing them to contribute to a number of reaction schemes.…”