A. Haas, C. Klare, P. Betz
Mar 27, 1996
Citations
0
Influential Citations
69
Citations
Journal
Inorganic Chemistry
Abstract
The syntheses of three acyclic (fluorosulfonyl)− or ((trifluoromethyl)sulfonyl)−nitrogen derivatives and their crystal and molecular structures are reported. The structures of bis((trifluoromethyl)sulfonyl)amine (1; (CF3SO2)2NH) and the corresponding anion in magnesium hexaaquo bis((trifluoromethyl)sulfonyl)amide dihydrate (2; [Mg(H2O)6][(CF3SO2)2N]2·2H2O) shed some light on the observed high gas-phase acidity of (CF3SO2)2NH. Extensive electron delocalization in the anion [(CF3SO)2N]- from planar, sp2-hybridized nitrogen into 3d orbitals of sulfur results in a noticeable shortening of the S−N bond on deprotonation. Similar electron delocalization is observed for the third compound, bis(bis(fluorosulfonyl)amino)sulfur (3; (FSO2)2NSN(SO2F)2), which features planar nitrogens with nearly six equidistant S−N bonds and extremely short S−O and S−F bonds. Compounds 2 and 3 have not been reported previously. Their unexpected, accidental formation and their characterization will be discussed. Compound 1 crystallize...