Arylsulfurdiimides: a new class of sulfur–nitrogen anion

Preparation and Structural Characterization of [K(18‐crown‐6)]+ Salts of [RNSN]− Anions and the [NSN]2− Dianion

“…The solid-state structures of the salts 1 and 3؊6 are shown in Figure 1 and Figures 2Ϫ5, respectively, and the details of the structure ) determinations are listed in Table 1. Selected bond lengths and bond angles are given in Ϫ family, [6,8] and the [NSN] 2Ϫ dianion (salt 6) are described for the first time. The X-ray structure of salt 2 was not Ϫ anion (salt 3) demonstrates the stereoelectronically unfavorable E-configuration (Figure 4), previously also observed for its TAS ϩ salt (for the in-depth discussion of the Z-and E-configurations and the bonding properties of the [RNSN] Ϫ anions, see refs.…”

Fluorinated 1,3λ4δ2,2,4‐Benzodithiadiazines − A Synthetic, Structural and Theoretical Study

“…Compounds 3Ϫ5 were obtained as black crystals. [25] 2,2Ј,3,3Ј,5,5Ј,6,6Ј-octafluorodiphenyl disulfide (21) [38] and 2,3,5,6-tetrafluoroaniline (23). [39] Starting Compound 17: The residue was distilled under vacuum, yielding, according to GC-MS and 19 F NMR, 0.35 g of a 2:1:6 mixture of 4,6,7-trifluoro-5-trifluoromethyl-2,1,3-benzothiadiazole (20), [25] 4,4Ј-bis(trifluoromethyl)-2,2Ј,3,3Ј,5,5Ј,6,6Ј-octafluorodiphenyl disulfide (22), [40] and 2,3,5,6-tetrafluoro-4-(trifluoromethyl)-aniline (24).…”

Reactions of Arylthiazylamides with Internal and External Fluoro Electrophiles − Formation of Products with Unusual Structures

“…We recently reported the preparation, isolation, and Xray structural characterization of (Me 2 N) 3 S ϩ (TAS ϩ ) salts of [RNSN] Ϫ anions (R ϭ Me 3 C, Me 3 Si, [1] various aryl substituents [2,3] ). It emerged from the X-ray data that due to the unexpectedly short terminal SN bond, these anions should be regarded as thiazylamide (A) rather than as sulfurdiimide (B) anions (Scheme 1), [1Ϫ3] in accordance with calculations at the MP2/6Ϫ31G* and B3LYP/6Ϫ311ϩG* levels of theory.…”

“…Thus, the [RNSN] Ϫ anions belong to the rare class of compounds featuring sulfurϪnitrogen triple bonds and therefore they deserve more detailed investigation. Scheme 1 Previously, some [RNSN] Ϫ anions (R ϭ Ar F ϪXϪ; X ϭ Ϫ, S) generated in situ in the form of Cs ϩ salts have been shown to be involved in intramolecular nucleophilic ortho cyclizations, which resulted in the previously unknown and otherwise inaccessible polyfluorinated 2,1,3-benzothiadiazoles (X ϭ Ϫ, Ar F ϭ 4-RC 6 F 4 ), [4] naphtho-[1,2-c]-and naphtho [2,3-c] [1,2,5]thiadiazoles (X ϭ Ϫ; composition (R = 4-Py F ) to 4-Py F NH 2 (6) or intramolecular cyclization (R = 2-Np F ) to the polyfluorinated thiadiazole 9. The compounds of types 4, 5, 8, and 9 have been characterized by single-crystal X-ray diffraction as having both Z,E and Z,Z configurations [8 and 9 as molecular complexes with C 10 F 8 and (Ph−N=) 2 S (5e), respectively, featuring π-stacking interactions of the arene−polyfluoroarene type].…”

“…[6] With Ar F ϭ 4-Py F and X ϭ Ϫ; S (4-Py F ϭ 2,3,5,6-tetrafluoro-4-pyridinyl), however, no heterocycles could be prepared, and polyfluorinated 4-aminopyridine was the major product instead. [7] It follows from the available data [4Ϫ7] that the reactivity of these intermediate anions toward internal electrophiles (ortho cyclization), as well as their stability, [1Ϫ3] depends strongly on the substituents at the NSN Ϫ moiety {whilst TAS ϩ [RNSN] Ϫ salts (R ϭ Me 3 C, Me 3 Si) are moderately stable at room temperature, [1] their R ϭ Ar analogues decompose rapidly at temperatures above Ϫ20°C [2,3] }.…”