期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 22, 页码 8452-8454出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja201569p
关键词
-
资金
- NSF [CHE 0841428]
- Direct For Mathematical & Physical Scien [0841428] Funding Source: National Science Foundation
- Division Of Chemistry [0841428] Funding Source: National Science Foundation
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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据