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-η2:η2-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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