Oligomeric carbocation-like species from protonation of chloroalkanes.
- Author(s): Stoyanov, Evgenii S
- Stoyanova, Irina V
- Reed, Christopher A
- et al.
Published Web Locationhttps://doi.org/10.1021/ja201569p
The protonation of chloroethane by the strongest known solid superacid, the carborane acid H(CHB(11)Cl(11)), has been studied by quantitative IR spectroscopic methods to track mass balance and uncover previously unobserved chemistry. In the first step, an intermediate EtCl·H(CHB(11)Cl(11)) species without full proton transfer to EtCl can be observed when d(5)-deuterated chloroethane is used. It rapidly eliminates HCl (but not DCl) to form ethyl carborane, Et(CHB(11)Cl(11)), which binds a second molecule of chloroethane to form the Et(2)Cl(+) chloronium ion. This undergoes a slower, previously unrecognized HCl elimination reaction to form a butyl carborane, Bu(CHB(11)Cl(11)), beginning an oligomerization process whereby unsymmetrical dialkylchloronium ions decompose to alkyl carboranes of formula Bu(C(2)H(4))(n)(CHB(11)Cl(11)) up to n = 4. Over time, a parallel competing process of de-oligomerization take place in the presence of free carborane acid that finishes with the formation of hexyl or butyl carboranes. Upon heating to 150 C, the final products are all converted to the remarkably stable tert-butyl cation carborane salt.