Stereoelectronic Source of the Anomalous Stability of Bis-peroxides

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2017 Aug 1

PMID 28757970

Citations 13

Authors

Gabriel Dos Passos Gomes

Vera Vil

Alexander Terentev

Igor V Alabugin

Affiliations

Soon will be listed here.

Abstract

The unusual stability of bis- and tris-peroxides contradicts the conventional wisdom - some of them can melt without decomposition at temperatures exceeding 100 °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 → σ* interactions that are absent in mono-peroxides but reintroduced in molecules where two peroxide moieties are separated by a CH group. Furthermore, such effects can be induced by other σ-acceptors and amplified by structural constraints imposed by cyclic and bicyclic frameworks.

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