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Published on: April 19, 2019
Stereoelectronic source of the anomalous stability of bis-peroxides
Gabriel Dos Passos Gomes1, Vera Vil'2, Alexander Terent'ev2
1Department of Chemistry and Biochemistry , Florida State University , Tallahassee , Florida 32306-4390 , USA . Email: ggomes@chem.fsu.edu ;
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.
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