Enthalpies of formation of cyclic alkyl peroxides: Dioxirane, 1,2-dioxetane, 1,2-dioxolane, and 1,2-dioxane

Document Type

Article

Publication Date

4-4-1997

Abstract

Enthalpies of formation of four cyclic alkyl peroxides are calculated using ab initio methods. The values are reported as: ΔH°f298(dioxirane) = -2.91 ± 1.34 kcal/mol, ΔH°f298(1,2-dioxetane) = 1.09 ± 0.51, ΔH°f298( 1,2-dioxolane) = -27.43 ± 0.91 kcal/mol, and ΔH°f298(1,2-dioxane) = -31.74 ± 0.96 kcal/mol. Enthalpies of formation for 1,2-dioxetane, 1,2-dioxolane, and 1,2-dioxane are calculated using isodesmic reactions at the MP4SDTQ/6-31G* * //MP2/6-31G* level of theory. These isodesmic reactions are 'group balanced'. For dioxirane, reaction energies of two reactions are calculated using the G2 method. The difference of ΔH°f298(dioxirane) values determined using these two reactions is within 0.7 kcal/mol. Ring strain energies (in kcal mol-1) are determined as 30.7, 26.7, 7.3, 4.0 for dioxirane, 1,2-dioxetane, 1,2-dioxolane, and 1,2-dioxane, respectively. Comparisons are also made with a scaled PM3 estimation, and results are in reasonable agreement with the recommended values.

Identifier

0031552316 (Scopus)

Publication Title

Chemical Physics Letters

External Full Text Location

https://doi.org/10.1016/S0009-2614(97)00168-1

ISSN

00092614

First Page

175

Last Page

179

Issue

1-2

Volume

268

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