X-ray structures and anionotropic rearrangements of Di-tert-butyl-substituted thiiranium and thiirenium ions. A structure-reactivity relationship.

The X-ray structures of c-2,t-3-di-tert-butyl-r-1-methylthiiranium 8 BF(4)(-), t-2,t-3-di-tert-butyl-r-1-methylthiiranium ion 10 BF(4)(-), and 2,3-di-tert-butyl-1-methylthiirenium 11 BF(4)(-) have been determined. The DeltaG()(298) values for the rearrangements from the cis and the trans tert-butyl groups of 8 SbCl(6)(-) to thietanium ion (two intramolecular S(N)2 displacements) and for the rearrangement of 11 SbCl(6)(-) to thietium ion (an intramolecular S(N)2-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.