Folgereaktionen von Sulfenen aus Sulfonylchloriden und tertiären Aminen, 3[1,2] Kristallstrukturanalyse von Bis(trimethylammoniosulfonyl)methanid‐tetraphenylborat. – n‐σ*‐Wechselwirkungen (Hyperkonjugation und Homohyperkonjugation) in Sulfen–Amin‐S,N‐Addukten

Secondary Reactions of Sulfenes from Sulfonyl Chlorides and Tertiary Amines, 3[1,2]. – Crystal Structure Analysis of Bis(trimethylammoniosulfonyl)methanide Tetraphenylborate. – n‐σ*‐Interactions (Hyperconjugation and Homohyperconjugation) in Sulfene – Amine S,N‐Adducts Bis(trimethylammoniosulfonyl)methanide chloride (3b) could be obtained in 97% yield by reaction of methanedisulfonyl dichloride (5) with three equivalents of trimethylamine. X‐ray analysis of the tetraphenylborate 3c reveals that the conformation of the cation is determined by nC‐σ*S–N interactions (negative hyperconjugation) and by nC‐σ*N–C interactions (negative homohyperconjugation). These effects were deduced from alterations of the bond lengths within the S–N–C chains which are coplanar to the occupied pz orbital at the central C atom. Comparison with known crystal structure data shows, that sulfene – amine S,N‐adducts generally have the zwitterionic ammoniosulfonylmethanide structure 3, stabilized by nC‐σ* interactions.