Gas phase structures of N-(fluorosulfonyl)imidosulfurous difluoride, FSO2NSF2, and N-(fluorosulfonyl)imidosulfuryl fluoride, FSO2NS(O)F2

The isolation, characterisation, gas phase electron diffraction and crystal structure of the thermally stable radical [CF3CSNSCCF3]˙ †

“…Both UB3PW91/6-31G* and UMPW1PW91/6-31ϩG* optimised geometries of radical 4d were in satisfactory agreement with the structure determined by electron diffraction and X-ray crystallography (Table 7), taking into account the known elongation of bonds containing heavier elements at this level of theory 59 (SN bonds calculated to be too long by 0.03 to 0.04 Å). The calculated energy of rotating the SNS fragment out of the SCCS plane is very low (e.g.…”

Structures and Conformations of ((Trifluoroacetyl)imido)(trifluoromethyl)sulfur Fluoride, CF3C(O)NS(F)CF3

“…In the prevailing anti-syn form the S-C bond is orientated antiperiplanar and the S-F bond nearly perpendicular with respect to the N-C bond (φ(CsNdSsC) ) -164(5)°and φ(CsNd SsF) ) 98(4)°). The NdS bond in 1 and 2 (1.549(5) and 1.554(8) Å, respectively) is much longer than that in imidosulfurous difluorides (1.48 ( 0.01 Å) [1][2][3][4][5][6][7] and in dichlorides (1.515 ( 0.005 Å). 8,9 The lengthening of this bond can be attributed partially to the lower electronegativity of the substituents and partially to the absence of anomeric interactions in the anti-syn conformer.…”

“…All imidosulfurous difluorides of the type RNdSF 2 with R ) Cl, 1 CF 3 , 2,3 NC, 4 FC(O), 5 CF 3 C(O), 6 and FSO 2 7 as well as imidosulfurous dichlorides with R ) CF 3 8 and FC(O) 9 possess syn conformation around the NdS double bond (see Chart 1). Although the anti form appears to be sterically more favorable, quantum chemical calculations predict its energy to be higher by about 5-10 kcal/mol than that of the syn conformer.…”

Anomeric Interactions in Pentafluoroethylimidosulfurous Dichloride, CF3CF2N=SCl2: Structural, Conformational and Configurational Properties in the Gaseous and Condensed Phases

“…Vibrational spectroscopy, gas electron diffraction, X‐ray crystallography, quantum chemical calculations, and other techniques have proved to be powerful tools to understand the structural properties of sulfur imide molecules containing fluorine atoms or fluorinated substituents groups. Thus, the structure and conformational and configurational properties of molecules of the type R F N=SF 2 [R F = CF 3 ,13–16 FC(O),17,18 NC,19 CF 3 C(O),20 and FSO 2 21,22] and R F N=SCl 2 [R F = CF 3 23,24 and FC(O)25] have been studied, all of which show only a ( Z ) configuration around the putative N=S double bond. It is interesting to note that compounds with different substituents attached at the sulfur atom of the N=S group favor the ( E ) form.…”