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Theoretical study on S H 2 reaction of methyl radical with three‐membered ring
Author(s) -
Zhang Xiang
Publication year - 2014
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24730
Subject(s) - chemistry , homolysis , ring (chemistry) , methyl radical , nucleophile , methyl group , computational chemistry , substitution reaction , nucleophilic substitution , radical nucleophilic aromatic substitution , radical , photochemistry , medicinal chemistry , nucleophilic aromatic substitution , group (periodic table) , organic chemistry , catalysis
Bimolecular homolytic substitution (S H 2) reactions of the methyl radical with a series of three‐membered ring compounds have been given a systematic theoretical study. These reactions proceed predominantly via the backside displacement. The formation of the new radical product is thermodynamically favorable probably due to the release of the ring strain. Natural bond orbital analysis reveals that SOMO → σ*(C‐X) (X= C, N, O) interaction plays a major role in these S H 2 reactions, which shows the methyl radical mainly acts as a nucleophilic radical. In addition, according to the activation strain model analysis, an expected single correlation has not been obtained between the reactant distortion enthalpies and the overall activation enthalpies. However, these reactions can be divided into three groups and each group exhibits a good linear correlation. Marcus theory can thoroughly account for this phenomenon. © 2014 Wiley Periodicals, Inc.