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https://doi.org/10.5562/cca3172

The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane

Ivana Antol
Mirjana Eckert-Maksić

Puni tekst: engleski, pdf (13 MB) str. 215-223 preuzimanja: 211* citiraj
APA 6th Edition
Antol, I. i Eckert-Maksić, M. (2017). The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane. Croatica Chemica Acta, 90 (2), 215-223. https://doi.org/10.5562/cca3172
MLA 8th Edition
Antol, Ivana i Mirjana Eckert-Maksić. "The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane." Croatica Chemica Acta, vol. 90, br. 2, 2017, str. 215-223. https://doi.org/10.5562/cca3172. Citirano 24.08.2019.
Chicago 17th Edition
Antol, Ivana i Mirjana Eckert-Maksić. "The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane." Croatica Chemica Acta 90, br. 2 (2017): 215-223. https://doi.org/10.5562/cca3172
Harvard
Antol, I., i Eckert-Maksić, M. (2017). 'The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane', Croatica Chemica Acta, 90(2), str. 215-223. https://doi.org/10.5562/cca3172
Vancouver
Antol I, Eckert-Maksić M. The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane. Croatica Chemica Acta [Internet]. 2017 [pristupljeno 24.08.2019.];90(2):215-223. https://doi.org/10.5562/cca3172
IEEE
I. Antol i M. Eckert-Maksić, "The Influence of Multiple Fluorination on the Ring Opening of [2.2.2]Propellane", Croatica Chemica Acta, vol.90, br. 2, str. 215-223, 2017. [Online]. https://doi.org/10.5562/cca3172

Sažetak
Effect of electronegative substituents on ring opening of [2.2.2]propellane was examined by quantum chemical calculations at CASSCF and CASPT2 level of theory. Comparison of the results with those obtained with MR-AQCC calculations indicated that calculations beyond CASSCF level were needed for reliable description of the process. Calculations show a strong effect of fluorination on the central bond elongation energy profile, with the effect being most pronounced for the perfluoro derivative. Moreover, for rearrangement of the most of multiply fluorinated derivatives, including perfluoro[2.2.2]propellane, CASPT2 calculations predict a single minimum potential energy well, which hampers rearrangement to significantly more stable fluorinated 1,4-dimethylenecyclohexane analogues. This observation is in harmony with high stability of synthetically available stable heavily fluorinated derivatives which, in contrast to the parent [2.2.2]propellane, do not rearrange to the thermodynamically most stable fluorinated 1,4-dimethylene-cyclohexane isomer.

Creative Commons License This work is licensed under a Creative Commons Attribution 4.0 International License.

Ključne riječi
Ab initio calculations; Grob rearrangement; isomerisation; [2.2.2]propellane; fluorination

Hrčak ID: 185768

URI
https://hrcak.srce.hr/185768

Posjeta: 292 *