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Trithiazyl trichloride
Chemical compound From Wikipedia, the free encyclopedia
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Trithiazyl trichloride is the inorganic compound with the formula (NSCl)3. A white solid, it is a precursor to other sulfur nitrides,[1] but has no commercial applications.
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Structure
The molecule is a 6-membered ring of alternating nitrogen and sulfur atoms, where each sulfur atom is attached to one chlorine atom by a single bond. The molecule contains alternating single and double bonds in the S3N3 core. The molecule has C3v symmetry. The S3N3 core is slightly ruffled structure with S-N distances of 160.5 pm. The S-Cl distances are 208 pm, and the chlorine atoms are mutually cis. The S centers are tetravalent and pyramidal. In contrast to the NSCl connectivity, nitrosyl chloride has the connectivity ONCl.[2][3]
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Synthesis and reactions
Trithiazyl trichloride is obtained by chlorination of tetrasulfur tetranitride or thiazyl fluoride monomer:[4]
- 3 S4N4 + 6 Cl2 → 4 (NSCl)3
- 3 FSN + 3 Cl2 → (NSCl)3 + 3 ClF
At 100 °C in vacuum, thiazyl chloride trimer undergoes cracking to thiazyl chloride monomer, which is a green gas.
- (−N=S(−Cl)−)3 → 3 N≡S−Cl
In N≡S−Cl, chlorine is bonded to sulfur, in contrast to nitrosyl chloride O=N–Cl, where chlorine is bonded to nitrogen. In contrast, with six fewer electrons, cyanuric chloride is a planar ring.
Alkoxide or silver salts displace the chlorides:[5]
- (-NS(Cl)-)3 + 3 NaOR → (-NS(OR)-)3 + 3 NaCl
- (-NS(Cl)-)3 + 3 AgX → (-NS(X)-)3 + 3 AgCl
Treating thiazyl chloride with sulfur in the presence of antimony pentachloride gives dithionitronium hexachloroantimonate:[6]
- SNCl + S + SbCl5 → [NS2]SbCl6
It reacts with nitriles to dithiadiazolium chlorides:[2]
- 6 RCN + 4 (NSCl)3 → 6 [RCN2S2]+Cl− + 3 Cl2 + 3 N2
Sulfur trioxide successively oxidizes the compound at the sulfur atoms to (NSOCl)3,[4] which exists as stereoisomers.
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References
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