Geometry and Conformation of Thietanium Ions from Diffraction Data and Ab Initio Calculations

Four‐membered ring thiosulfonium ions may be obtained quantitatively and under mild conditions by anionotropic rearrangement of C‐(tert‐butyl)‐substituted thiiranium ion precursors. Thus, t‐4‐(tert‐butyl)‐r‐1,2,2,c‐3‐tetramethylthietanium tetrafluoroborate or hexachloroantimonate ( 2a or 2b , resp.) were formed from thiiranium ion 1 . The thietanium salts 2a and 2b were characterized by X‐ray crystal‐structure analysis. Their cation geometry was also optimized by ab initio calculations at the RHF/6‐31G*//RHF/6‐31G* level, as were those of its stereoisomer 3 and of the unsubstituted S‐methylthietanium ion 5 . Comparison of 2 , 3 , and 5 with 4 – the only other thietanium ion studied by XRD, where the C‐atoms of the thioniacyclobutane ring are part of a trinorbornane skeleton – indicates that, in these systems, relief from substituent overcrowding is easily achieved by a folding of the four‐membered ring along the line connecting the two opposite C‐atoms. The corresponding ring‐deformation normal mode has a calculated frequency as low as 109 cm⁻¹ in ion 5 , to be compared with a frequency of 138 cm⁻¹ in methylcyclobutane. For thietanium ion 2 , the frequencies of the two normal modes involving such ring deformation have calculated values of 61 and 85 cm⁻¹.