Tetrasulfur Tetranitride - Acid-base Reactions

Acid-base Reactions

S4N4 serves as a Lewis base by binding through nitrogen to strongly Lewis acidic compounds such as SbCl5 and SO3. The cage is distorted in these adducts, thus delocalization of electrons may be disrupted.

S4N4 + SbCl5 → S4N4·SbCl5
S4N4 + SO3 → S4N4·SO3

The reaction of with S4N4 is reported to form a complex where a sulfur forms a dative bond to the metal. This compound upon standing is isomerised to a complex in which a nitrogen atom forms the additional bond to the metal centre.

It is protonated by HBF4 to form a tetrafluoroborate salt:

S4N4 + HBF4 → [BF−
4]

The soft Lewis acid CuCl forms a polymer containing intact S4N4 rings as the bridging ligands:

n S4N4 + n CuCl → (S4N4)n-μ-(-Cu-Cl-)n

S4N4 is sensitive to hydrolysis in the presence of base. Dilute NaOH hydrolyzes S4N4 as follows, yielding thiosulfate and trithionate:

2 S4N4 + 6 OH− + 9 H2O → S2O2−
3 + 2 S3O2−
6 + 8 NH3

More concentrated base yields sulfite:

S4N4 + 6 OH− + 3 H2O → S2O2−
3 + 2 SO2−
3 + 4 NH3

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