TY - JOUR
T1 - Cyanobenzyl and chlorobenzyl radicals via anion photoelectron imaging spectroscopy
AU - Dixon, Andrew R.
AU - Khuseynov, Dmitry
AU - Sanov, Andrei
N1 - Funding Information:
This work was supported by the U.S. National Science Foundation (grant CHE-1266152 ). A.R.D. acknowledges the partial support of the State of Arizona TRIF Imaging Fellowship.
Publisher Copyright:
© 2014 Elsevier B.V. All rights reserved.
PY - 2014/10/20
Y1 - 2014/10/20
N2 - We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 ± 0.01 eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. From these results, the C-H bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9 ± 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.
AB - We report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 ± 0.01 eV, determined from a combination of the experiment and theory, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. From these results, the C-H bond dissociation energies at the benzyl-α sites of the corresponding closed-shell parent molecules are determined: 80.9 ± 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions and in relation to other similar molecules.
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U2 - 10.1016/j.cplett.2014.09.001
DO - 10.1016/j.cplett.2014.09.001
M3 - Article
AN - SCOPUS:84907678855
SN - 0009-2614
VL - 614
SP - 72
EP - 77
JO - Chemical Physics Letters
JF - Chemical Physics Letters
ER -