P-S cage compounds

 Structure of cage compounds:

X-ray structure of P4S3

Colour code: S yellow; P Brown
 P-S cage compounds
 The structures of the phosphorous sulfides appear to be closely related to those of the
oxides, but there are some notable differences, e.g. P4O6 and P4S6 are not isostructural.
The bond distances within the cages of all the sulfides indicate single PP and PS
bonds; the data for P4S3 shown in Figure are typical. The terminal PS bonds are shorter
than those in the cage (e.g. 191 versus 208pm in P4S10).
 P-S cage compounds
Preparation:
 Above 570 K, white phosphorus combines with sulfur to give P4S10 which is the most
useful of the phosphorus sulfides.

 The reaction of red phosphorus with sulfur above 450K yields P4S3

 P4S7 can also be made by direct combination under appropriate conditions.

 P4S6 prepared by abstraction of Sulfur from P4S7 using PPh3

 P4S9 prepared by treatment of a phosphorus sulfide with sulfur

 -P4S5 prepared by treatment of a phosphorus sulfide with phosphorus

 P-S cage compounds
Preparation:
 -P4S5 prepared by treatment of a phosphorus sulfide with phosphorus

 -P4S4 prepared by reaction of  - or  -P4S3I2 with (Me3Sn)2S

Properties:
 P4S10 is a thiating agent (i.e. one that introduces sulfur into a system) in
organic reactions, and is a precursor to organothiophosphorus compounds.
 Phosphorus sulfides ignite easily, and P4S3 is used in ‘strike anywhere’
matches; it is combined with KClO3, and the compounds inflame when
subjected to friction. whereas P4S3 is stable to water, other phosphorus
sulfides are slowly hydrolysed
 P-S cage compounds
Properties:

 When P2S5 is heated under vacuum with Cs2S and sulfur in a 1 :2 :7 molar
ratio, Cs4P2S10 is formed. This contains discrete [P2S10]4- ions, the terminal
PS bonds in which are shorter (201 pm) than the two in the central chain
(219 pm).

[P2S10]4- ion