Stereoelectronic source of the anomalous stability of bis-peroxidesстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 2 ноября 2016 г.
Аннотация:The unusual stability of bis- and tris-peroxides contradicts the conventional wisdom-some of them can melt without decomposition at temperatures exceeding 100 degrees C. In this work, we disclose a stabilizing stereoelectronic effect that two peroxide groups can exert on each other. This stabilization originates from strong anomeric n(O) -> sigma(CO)* interactions that are absent in mono-peroxides but reintroduced in molecules where two peroxide moieties are separated by a CH2 group. Furthermore, such effects can be induced by other s-acceptors and amplified by structural constraints imposed by cyclic and bicyclic frameworks.