Solvolysis of (Z)-5-trimethylstannyl 2-adamantyl p-bromobenzenesulfonate: mechanistic implications of a record-breaking secondary alpha-deuterium kinetic isotope effect for an SN1 substrate |
| |
Authors: | Adcock William Trout Neil A Vercoe David Taylor Dennis K Shiner V J Sorensen Ted S |
| |
Affiliation: | School of Chemistry, Physics, and Earth Sciences, Flinders University of South Australia, Adelaide, SA 5001, Australia. william.adcock@flinders.edu.au |
| |
Abstract: | The secondary alpha-deuterium kinetic isotope effect (alpha-kie) for the solvolysis of (Z)-5-trimethylstannyl 2-adamantyl p-bromobenzenesulfonate in 97% w/w aqueous 2,2,2-trifluoroethanol (97T) at 25 degrees C has been measured (k(H)/k(D) = 1.33). The alpha-kie is abnormally high compared to the value of 1.23 for the corresponding limiting S(N)1 solvolysis of 2-adamantyl p-bromobenzenesulfonate, which proceeds via an extended ion-pair mechanism. A novel mechanism for the solvolysis of the tin compound is proposed that accommodates not only the high alpha-kie but also the absence of internal return. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|