Issue 12, 2015

Stereoelectronic source of the anomalous stability of bis-peroxides

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 nO → σ*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 σ-acceptors and amplified by structural constraints imposed by cyclic and bicyclic frameworks.

Graphical abstract: Stereoelectronic source of the anomalous stability of bis-peroxides

Supplementary files

Article information

Article type
Edge Article
Submitted
03 Jul 2015
Accepted
03 Sep 2015
First published
07 Sep 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 6783-6791

Author version available

Stereoelectronic source of the anomalous stability of bis-peroxides

G. D. P. Gomes, V. Vil', A. Terent'ev and I. V. Alabugin, Chem. Sci., 2015, 6, 6783 DOI: 10.1039/C5SC02402A

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