Sulfur-Nitrogen Compounds

Dr. Akhilesh Kumar Gupta

Sulfur-Nitrogen Compounds
Sulfur–nitrogen compounds Sulfur–nitrogen chemistry is an area
that has seen major developments over the last few decades, in
part because of the conductivity of the polymer (SN)x. The
following discussion is necessarily selective, and more detailed
accounts are listed at the end of the chapter. Probably the best
known of the sulfur–nitrogen compounds is tetrasulfur
tetranitride, S4N4. It has traditionally been obtained using reaction
16.120, but a more convenient method is reaction 16.121.
Tetrasulfur tetranitride is a diamagnetic orange solid (mp 451 K) which
explodes when heated or struck. Pure samples are very sensitive (see
exercise 1 at the end of the section). It is hydrolysed slowly by water (in
Synthesis of tetrasulfur tetranitride (S4N4) CCl4 (250 mL) and S2Cl2 (40 mL, 0.5 mol)
were added to a 500 mL three-necked flask at 00C with stirring. Afterwards, dry NH3
was introduced into the three-necked flask at a flow rate of 1200 mL min-1 . The
whole reaction was carried out in an ice bath for 1 hour, resulting in the
appearance of an orange precipitate in a red solution. The precipitate was washed
with pure water with stirring for approximately 3 hours, isolated by Soxhlet
extraction with dry dioxane, and then recrystallized from benzene to obtain pure
S4N4 crystals. To generate S4N4 crystals, the red solution was transferred to a
vacuum after evaporation treatment with dichloromethane and recrystallized with
benzene.
Synthesis of thiazyl trifluoride S4N4 (3.7 g, 0.02 mol) and CCl4 (80 mL) were added to
a copper reactor equipped with a copper reflux condenser under N2 protection.
The mixture was dissolved under magnetic stirring and heated to stable reflux.
Then, AgF2 (45.7 g, 0.32 mol) was quickly added to the reflux. The whole reaction
was carried out at 780C for 2 hours. The outlet of the condenser was connected by
a conduit, and the gas product was successively dried by potassium permanganate
solution and anhydrous calcium chloride and finally condensed to obtain crude
NSF3 as the product. The purity of NSF3 was 90.6%, as determined by GC, while the
structure was confirmed by IR and GC-MS.
RSC Adv., 2020, 10, 2740 Received 7th November 2019 Accepted 8th January
2020 DOI: 10.1039/c9ra09256k rsc.li/rsc-advances 2740 | RSC Adv., 2020, 10,
2740–2746 This journal is © The Royal Society of Chemistry 2020 RSC Advances
PAPER
Reactivity

S4N4 exhibits a wide range of reactivity, but what is interesting is its

utility as a precursor to other S-N compounds:
What is worth specially mentioning is the reaction between S 4N4 and
Ag - S4N4 first reacts with Ag to form Ag2S, which it turn catalyzes the
depolymerization of S4N4 into S2N2, the precursor for (SN)x as shown
above, in situ.

On top of the map above, S4N4 can also be chlorinated at the

"cradlehead" sulfurs, or form an adduct with BF3 using its nitrogens.
S4N4 can be thought of as 4 Ns arranged in a plane with a tetrahedron of 4
S cutting through the plane. The point group of the molecule is D 2d.

The sulfurs that occupy the opposite ends of the "cradle" to each other have
some degree of transannular bonding interactions as they are closer to
each other than nonbonding Van Der Waals interactions would suggest.

All S-N bonds in the molecule are of equal length, and are shorter than
typical S-N bonding in molecules. This is attributed to some extent of
electron delocalization in the heterocycle.