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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
Author(s) -
Opitz Günter,
Wiehn Walter,
Ziegler† Manfred L.,
Nuber Bernhard
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250717
Subject(s) - chemistry , tetraphenylborate , adduct , crystal structure , medicinal chemistry , hyperconjugation , amine gas treating , stereochemistry , trimethylamine , crystallography , molecule , organic chemistry , ion
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 n C ‐σ * S–N interactions (negative hyperconjugation) and by n C ‐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 p z 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 n C ‐σ * interactions.