Stereoelectronic source of the anomalous stability of bis-peroxides

Stereoelectronic source of the anomalous stability of bis-peroxides Full article

Journal

Chemical Science
ISSN: 2041-6520 , E-ISSN: 2041-6539

Output data

Year: 2015, Volume: 6, Number: 12, Pages: 6783-6791 Pages count : 9 DOI: 10.1039/c5sc02402a

Authors

Gomes Gabriel dos Passos ¹ , Vil' Vera ² , Terent'ev Alexander ² , Alabugin Igor V. ¹

Affiliations

1	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospekt, Moscow 119991, Russian Federation

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.

Gomes G.d.P. , Vil' V. , Terent'ev A. , Alabugin I.V.
Stereoelectronic source of the anomalous stability of bis-peroxides
Chemical Science. 2015. V.6. N12. P.6783-6791. DOI: 10.1039/c5sc02402a WOS Scopus OpenAlex

≡ Web of science:	WOS:000365225300011
≡ Scopus:	2-s2.0-84946712641
≡ OpenAlex:	W1781171056