Reactions of trifluorocyclotrithiazene (S3N3F3) and trichlorocyclotrithiazene (S3N3Cl3) with Lewis acids. Preparation and crystal structure of pentathiazyl hexachloroantimonate (S5N5)(SbCl6)

Abstract

The reactions of S3N3C13 with SbCIS and the reactions of S3N3F3 with AsF,, SbFS, and SO3 have been studied. The reaction of S3N3C13 with SbC1, in a 1:2 mole ratio gave (S4N4)(SbC16)2 as the major product in SO2, CH2C12, and S0C12 as solvents.With a 1:l mole ratio and CH2C12 as solvent the products were (SSNS)(SbCl6) and S4N4.SbCIs. This mixture reacted with additional SbCIS to give (S4N4)(SbC16)2. Both (SSNS)(SbCl6) and S4N4.SbCIs were characterized by X-ray crystallography. The geometry of the planar pentathiazyl cation SSN5+ is intermediate between the "azulene-like" and heart-shaped conformations found previously for other examples of this cation. This is attributed to disorder in part of the cation. The reactions of S3N3F3 with AsFS, SbF,, and SO3 in the mole ratios 1:6, 1:6, and 1:3 gave the thiazyl salts SN(AsF,), SN(Sb2F1,), and SN(S03F), respectively.

Bonding Trends in Lewis Acid Adducts of S4N4 – X‐ray Structure of TeCl4·S4N4

“…[3] [f] Ref. [6] [g] Ref. [19] with respect to the identity of MX n , and therefore play a role in the stabilities of the adducts.…”

“…The crystal structures are known for BF 3 ·S 4 N 4 , [1] SO 3 ·S 4 N 4 , [2] AsF 5 ·S 4 N 4 , [3] SbCl 5 ·S 4 N 4 , [4][5][6] FeCl 3 ·S 4 N 4 , [7,8] TaCl 5 ·S 4 N 4 , [9] and TiCl 4 ·S 4 N 4 . [10] The complexes SnCl 4 ·2S 4 N 4 [11] and TiCl 4 ·2S 4 N 4 [10] exemplify structurally characterized adducts with a 1:2 stoichiometry.…”

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

“…Electron precise S 3 N 3 3+ is unstable due to low ΔE elstat arising among the positively charged fragments and electron rich S 3 N 3 + and S 3 N 3 − are rather stable, whereas electron rich C 6 H 6 2− and C 6 H 6 4− are unstable due to low ΔE elstat among the negatively charged fragments and prefers electron‐precise C 6 H 6 instead. The stability of other electron‐rich sulfur‐nitrogen compounds/ions such as S 2 N 2 ,− S 2 N 3 + , S 4 N 3 + , S 4 N 4 2+ , S 5 N 5 + , could be a hint that the poor electrostatic component among the fragments of electron precise cyclic sulfur‐nitrogen compounds might play a crucial role for their instability.…”

Structures of the Phosphazenes [ClC(NPCl3)2]+PCl6 − and [CH3C(NPCl3)2]+SbCl6 − at 90 K

“…A search of the Inorganic Crystal Structure Database (Bergerhoff & Brown, 1987) for PC16-anions [five hits; the disordered compounds (PCln)3TiC16PC16 (Shamir, Schneider, Bino & Cohen, 1986) and (PC14)3SnC16PC16 (Shamir, Luski, Bino, Cohen & Gibson, 1985) were ignored] and SbC16 anions [38 hits; the wrong cell constant b = 56.72 (1)A in SsNsSbC16 (Gillespie, Sawyer, Slim & Tyrer, 1982) was corrected to b = 46.72 (1) A] yielded mean distances of 2.127 (4) and 2.365 (1) A, respectively. A search of the Inorganic Crystal Structure Database (Bergerhoff & Brown, 1987) for PC16-anions [five hits; the disordered compounds (PCln)3TiC16PC16 (Shamir, Schneider, Bino & Cohen, 1986) and (PC14)3SnC16PC16 (Shamir, Luski, Bino, Cohen & Gibson, 1985) were ignored] and SbC16 anions [38 hits; the wrong cell constant b = 56.72 (1)A in SsNsSbC16 (Gillespie, Sawyer, Slim & Tyrer, 1982) was corrected to b = 46.72 (1) A] yielded mean distances of 2.127 (4) and 2.365 (1) A, respectively.…”