Crystal Structure of Burgess Inner Salts and their Hydrolyzed Ammonium Sulfaminates*
Anthony J. ArduengoA Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, AL 35487-0336, USA.
B Department of Chemistry, School of Science, Kitasato University, 1-15-1 Kitasato, Minami-ku, Sagamihara, Kanagawa, 252-0373, Japan.
C Corresponding author. Email: aj@ajarduengo.net
Australian Journal of Chemistry 72(11) 867-873 https://doi.org/10.1071/CH19338
Submitted: 21 July 2019 Accepted: 29 July 2019 Published: 23 August 2019
Abstract
The solid-state structures of the Burgess reagent, and its analogous ethyl ester reveal structures indicative of triethylamine solvated sulfonyl imides rather than the more commonly depicted triethylammonium sulfonyl amidate. The existence of a reversibly formed hydrate of Burgess reagent is not supported by present studies, but rather a hydrosylate that does not revert to the Burgess reagent with gentle warming under vacuum was isolated and characterised. Structures of the hydrosylates from both the methyl- and ethyl-amidate esters were determined from X-ray crystallographic analysis and are reported. The crystal structures of the Burgess inner salts exhibit geometries at the sulfur atoms that are intermediate between a planar O2S=NCO2R unit and tetrahedral 4-coordinate sulfur centres that would be expected from a strong single (dative) bond between the triethylamine nitrogen and sulfur. The hydrolysed ammonium sulfaminates are water soluble intermolecular salts composed of triethylammonium ions, Et3NH+, and N-(alkoxycarbonyl)sulfaminate, O(−)SO2NHCO2R {R = CH3 or C2H5}.
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