Theoretical study of disproportionation reaction of fluorinated ethylenes

• Published in: Journal of fluorine chemistry Vol. 200; pp. 133 - 141
• Main Authors: Fukaya, Haruhiko, Hayakawa, Yoshio, Okamoto, Hidekazu, Ueno, Katsuya, Otsuka, Tetsuo
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01-08-2017; Elsevier BV
• Subjects: Chemical synthesis; Chlorofluorocarbon; Computational chemistry; Density functional theory; Dimerization; Disproportionation; Ethylene; Fluorination; Fluorine; Global warming; Natural bond orbital theory; Tetrafluoroethylene; Computational chemistry; Chlorofluorocarbon; Density functional theory; Global warming; Natural bond orbital theory
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2017.07.002

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•The disproportionation mechanism of fluorinated ethylenes such as tetrafluoroethylene and trifluoroethylene is proposed.•The disproportionation reaction is most likely initiated by dimerization of fluorinated ethylenes to produce a 1,4-biradical intermediate.•At elevated temperatures, rearrangement of fluorinated ethylenes and 1,4-biradical intermediates takes place, and a stable final product, CF4, is formed.
Single, two, and three-molecular reactions of fluorinated ethylenes such as tetrafluoroethylene and trifluoroethylene were computationally investigated to reveal the disproportionation mechanism. A plausible disproportionation path initiated by dimerization of ethylenes to produce a 1,4-biradical intermediate is described.