Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Applied and Materials
Ab Initio Calculation on the Reaction Mechanism of “Radical-Controlled” Oxidative Polymerization of Phenols
Masaaki KubotaAkinobu ShigaHideyuki HigashimuraKiyoshi FujisawaYoshihiko Moro-okaHiroshi UyamaShiro Kobayashi
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2004 Volume 77 Issue 4 Pages 813-818


Ab initio calculation on the reaction mechanism of “radical-controlled” oxidative polymerization (RCOP) of phenol catalyzed by μ-η22-peroxo dicopper(II) complex (1) was performed. The key step is the reaction of 1 with phenol, for which two reaction routes have been postulated. One is through phenoxo copper(II) intermediate (route X), and the other is via the abstraction of hydrogen atoms from phenol (route Y). All structures of the possible intermediates in both routes were optimized, and the energy profiles of these routes were compared with each other. For the reaction of 1 with phenol, route X would be favored more than route Y based on the present calculation results and previous experimental data. In comparison, the reaction of 1 with 2,4-di-t-butylphenol, which has a bulky substituent at the o-position, was evaluated in a similar manner. Route X may also be possible in this reaction.

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© 2004 The Chemical Society of Japan
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