Naslov
The influence of multiple fluorination on alleged valence isomerisation of [2.2.2]propellanes

Autori
Antol, Ivana ; Eckert-Maksić, Mirjana ; Maksić, Zvonimir B.

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
Ninth Triennial Congress of the World Association ot Theoretical and Computational Chemists / Yáñez, Manuel ; Mó, Otilia - Santiago de Compostela, 2011, PI-173

Skup
Ninth Triennial Congress of the World Association ot Theoretical and Computational Chemists

Mjesto i datum
Santiago de Compostela, Španjolska, 17.07.2011. - 23.07.2011

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
bond-stretch isomerism; Grob-type fragmentation; propellanes; multiple fluorination

Sažetak
The study of the bond-stretch isomerisation in [2.2.2]propellane [ ], as a classic example suggested by R. Hofmann, was extended to its multiple fluorinated derivatives. Namely, the parent [2.2.2]propellane was not synthesised in spite of the large barrier along the reaction pathway of ca. 20 kcal mol-1, which leads to the more stable open diradical isomer that easily rearranges to 1, 4-dimethylene-cyclohexane [ ]. The existence of stable heavily fluorinated derivative 4 suggests a strong effect of fluorination on the central bond elongation reaction energy profile. Indeed, CASPT2/cc-pVDZ//CAS(2, 2)/cc-pVDZ calculations show that perfluoro[2.2.2]propellane 3 and multiply fluorinated derivatives 2 and 4 have a single minimum potential energy well, which hampers rearrangement to significantly more stable fluorinated 1, 4-dimethylenecyclohexane analogues.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA