biostudies-literatureGomes GDPDivision of ChemistryFlorida State University6783-6791https://www.ebi.ac.uk/biostudies/studies/S-EPMC5508698biostudies-literatureUnknown6(12)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_O → 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.Chemical scienceStereoelectronic source of the anomalous stability of bis-peroxides.PMC5508698CHE-1465142Gomes GDPTerent'ev AVil' VAlabugin IVfalseStereoelectronic source of the anomalous stability of bis-peroxides.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_O → 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.2015-01-01T00:00:00Z2015 Dec2025-04-18T20:41:55.268Z2019-03-27T02:50:18ZS-EPMC55086982875797010.1039/c5sc02402a