Superacid-Promoted Ionization of Alkanes Without Carbonium Ion Formation: A Density Functional Theory Study
2012 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 116, no 40, 9979-9984 p.Article in journal (Refereed) Published
The carbonium ion has been suggested to be the intermediate in superacid-promoted reactions (SbF5-HF) such as hydrogen-deuterium exchange and in the electrophilic C-H cleavage into hydrogen and the carbenium ion. In this study, the superacid-promoted C-H cleavage into hydrogen and the carbenium ion was studied using density functional theory (B3LYP and M062X) and ab initio methods (MP2 and CCSD). The calculations suggest that the superacid-promoted C-H cleavage proceeds via a concerted transition state leading to hydrogen (H-2) and the carbenium ion without the formation of the elusive carbonium ion. The reactivity for the superacid promoted C-H cleavage decreases upon going from isobutane (tertiary) > propane (secondary) > isobutane (primary) > propane (primary) > ethane >> methane.
Place, publisher, year, edition, pages
2012. Vol. 116, no 40, 9979-9984 p.
Organic Chemistry Theoretical Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-181675DOI: 10.1021/jp306319sISI: 000309648800023OAI: oai:DiVA.org:uu-181675DiVA: diva2:557357