title: 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.
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.
authors.affiliation: School of Chemistry, Physics, and Earth Sciences, Flinders University of South Australia, Adelaide, SA 5001, Australia. william.adcock@flinders.edu.au
authors.forename: William
authors.initials: W
authors.lastname: Adcock
authors.forename: Neil A
authors.initials: NA
authors.lastname: Trout
authors.forename: David
authors.initials: D
authors.lastname: Vercoe
authors.forename: Dennis K
authors.initials: DK
authors.lastname: Taylor
authors.forename: V J
authors.initials: VJ
authors.lastname: Shiner
authors.forename: Ted S
authors.initials: TS
authors.lastname: Sorensen