A theoretical study of alkane protonation in HF/SbF5 superacid system

• Autor(a) principal: Esteves,Pierre M.
• Data de Publicação: 2000
• Outros Autores: Ramírez-Solís,Alejandro, Mota,Claudio J. A.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Journal of the Brazilian Chemical Society (Online)
• Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532000000400003
• topic: superacid; carbonium ions; alkane; DFT

Ab initio calculations for the protonation of the C-H and C-C bonds of methane, ethane, propane and isobutane by a superacid moiety was carried out. For the C-H protonation (H/H exchange) the transition state resembles an H-carbonium ion coordinated with the superacid. The activation energy for the H/H exchange was about 16 kcal.mol-1, at B3LYP/6-31++G** + RECP (Sb) level, regardless the type of C-H bond being protonated. For the C-C protonation the activation energy depends on the structure of the hydrocarbon and was always higher than the activation energy for C-H protonation, indicating a higher steric demand.