ISSN:
0009-2940
Keywords:
Bis(trimethylammoniosulfonyl)methanide tetraphenylborate
;
Sulfene-amine adducts
;
Hyperconjugation, negative
;
Homohyperconjugation, negative
;
n-σ* interactions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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-AdductsBis(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.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250717
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