%0 Journal Article
%A Destro, Riccardo
%A Lucchini, Vittorio
%A Modena, Giorgio
%A Pasquato, Lucia
%D 2000
%T X-ray Structures and Anionotropic Rearrangements of
Di-tert-butyl-Substituted Thiiranium and Thiirenium Ions. A
Structure−Reactivity Relationship
%U https://acs.figshare.com/articles/journal_contribution/X-ray_Structures_and_Anionotropic_Rearrangements_of_Di-_i_tert_i_-butyl-Substituted_Thiiranium_and_Thiirenium_Ions_A_Structure_Reactivity_Relationship/3720507
%R 10.1021/jo991731o.s001
%2 https://acs.figshare.com/ndownloader/files/5812203
%K butyl groups
%K trans tert
%K thietanium ion
%K BF
%K thietium ion
%K Anionotropic Rearrangements
%K steric hindrance
%K 8 SbCl 6
%K Thiirenium Ions
%K 11 SbCl 6
%K methylthiiranium
%K rearrangement
%K intramolecular S N 2 displacements
%X The X-ray structures of c-2,t-3-di-tert-butyl-r-1-methylthiiranium 8 BF4-, t-2,t-3-di-tert-butyl-r-1-methylthiiranium ion 10 BF4-, and 2,3-di-tert-butyl-1-methylthiirenium 11 BF4- have been
determined. The ΔG⧧298 values for the rearrangements from the cis and the trans tert-butyl groups
of 8 SbCl6- to thietanium ion (two intramolecular SN2 displacements) and for the rearrangement
of 11 SbCl6- to thietium ion (an intramolecular SN2-Vin displacement) are linearly correlated with
the strengths of the C−S breaking bonds, suggesting that the two mechanisms are, in the absence
of steric hindrance, uniquely governed by the nucleofugality of the sulfonium leaving group.
%I ACS Publications