Theoretical studies on the reaction mechanism of ketene dimerization reactions

The dimerization reactions of ketene in the gas phase to form cyclobutane-1,3-dione, diketene, or 2,4-dimethylene-1,3-dioxetane have been studied theoretically. The geometries of the reactants, products and the transition states of the above three reactions are optimized by an ab initio method. Sing...

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Bibliographic Details
Published in:Journal of molecular structure. Theochem 1988-06, Vol.167 (3), p.349-358
Main Authors: Fu, Xiaoyuan (X.Y.Fu), Fang, Decai, Ding, Yanbo
Format: Article
Language:English
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Summary:The dimerization reactions of ketene in the gas phase to form cyclobutane-1,3-dione, diketene, or 2,4-dimethylene-1,3-dioxetane have been studied theoretically. The geometries of the reactants, products and the transition states of the above three reactions are optimized by an ab initio method. Single point energies are obtained at the MP2/4–31G level, using STO-3G geometries. The calculated activation barriers are 29.8, 35.1 and 61.2 kcal mol −1, respectively. The orbital symmetry rule and frontier molecular orbital theory are used to elucidate the modes of approach of the reactants. In addition, the intrinsic reaction coordinate (IRC) based on the MINDO/3 method is used to trace the reaction pathways. No intermediate is found along the IRC of any reaction. All the reactions are concerted ones.
ISSN:0166-1280
1872-7999
DOI:10.1016/0166-1280(88)80238-0