Cyanobenzyl and chlorobenzyl radicals via anion photoelectron imaging spectroscopy

Abstract

We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN)=1.90±0.01eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl)≤1.12eV. From these results, the CH bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9±2.3kcalmol−1 for benzyl nitrile and an upper limit of 84.2kcalmol−1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.