Thiophosphate
Thiophosphates (or phosphorothioates, PS) are chemical compounds and anions with the general chemical formula PS
4−xO3−
x (x = 0, 1, 2, or 3) and related derivatives where organic groups are attached to one or more O or S. Thiophosphates feature tetrahedral phosphorus(V) centers.[1]
Organic
Organothiophosphates are a subclass of
-
Zinc dialkyldithiophosphate, an oil additive.[2]
-
Phosphorothioates are the basis for antisense therapies.
-
Amifostine, which is used in cancer chemotherapy.
-
Chlorpyrifos, a popular insecticide.
-
Malathion, a popular insecticide.
Oligonucleotide phosphorothioates (OPS) are modified oligonucleotides where one of the oxygen atoms in the phosphate moiety is replaced by sulfur. They are the basis of antisense therapy, e.g., the drugs fomivirsen (Vitravene), oblimersen, alicaforsen, and mipomersen (Kynamro).[3]
Inorganic
The simplest thiophosphates have the formula [PS4−xOx]3−. These trianions are only observed at very high pH, instead they exist in protonated form with the formula [HnPS4−xOx](3−n)− (x = 0, 1, 2, or 3 and (n = 1, 2, or 3).
Monothiophosphate
Monothiophosphate is the anion [PO3S]3−, which has C3v
Dithiophosphates
Dithiophosphate has the formula [PO2S2]3−, which has C2v
- P2S5 + 6 NaOH → 2 Na3PO2S2 + H2S + 2 H2O
Dithiophosphoric acid is obtained by treatment of barium dithiophosphate with sulfuric acid:
- Ba3(PO2S2)2 + 3 H2SO4 → 3 BaSO4 + 2 H3PO2S2
Both Na3PO2S2 and especially H3PO2S2 are prone toward hydrolysis to their monothio derivatives.
Tri- and tetrathiophosphates
Trithiophosphate is the anion [POS3]3−, which has C3v symmetry. Tetrathiophosphate is the anion [PS4]3−, which has Td symmetry.
PxSy: binary thiophosphates and polyphosphates
A number of these anions known. Some have attracted interest as components in
- PS−
3 is the analogue of the nitrate ion, NO−
3 (there is no PO−
3 analogue); it was isolated as the yellow tetraphenylarsonium salt[8] - PS3−
4 is the sulfur analogue of PO3−
4, and like PO3−
4 is tetrahedral. - P
2S4−
7 the pyrothiophosphate ion consisting of two corner sharing PS4 tetrahedra, analogous to the pyrophosphates.[9] - P
2S4−
10 An ion which can be visualised either as two PS4 tetrahedra joined by a disulfide link or a pyrothiophosphate where the bridging −S− is replaced by −S4−.[10] - P
2S2−
6 edge-shared bitetrahedral structure. The structure is therefore similar to the isoelectronic Al2Cl6 dimer. The oxygen analogue, dimetaphosphate P
2O2−
6, in contrast, is not known, the metaphosphates favour polymeric structures of chains or rings.[9] - P
2S2−
8 and P
2S2−
10 are related to P
2S2−
6 but their two bridging −S− atoms are replaced by −S−S− in P
2S2−
8 and by an −S−S−S− bridge in P
2S2−
10.[11] - P2S4−
6 These form water-stable salts.[12] The anion has an ethane-like structure and contains a P−P bond. The formal oxidation state of phosphorus is +4. The oxygen analogue is the hypodiphosphate anion, P
2O4−
6. - P
3S3−
9 contains a six-membered P3S3 ring. The ammonium salt is produced by reaction of P4S10 in liquid ammonia.[13] Another way of visualising the structure is that it is the P4S10 adamantane (P4O10) structure with a PS3+ vertex removed. - P
4S4−
8 contains a square P4 ring,[8] P
5S5−
10 contains a P5 ring and P
6S6−
12 a P6 ring.[11] These (PS−
2)
n cyclic anions contain P with an oxidation state +3. Note they are not trigonal as arsenic(III) is in arsenites, but are tetrahedral with two bonds to other phosphorus atoms and two to sulfur. The P
6S6−
12 anion is analogous to the P
6O6−
12 ring anion.[14] - P
4S2−
2 An unusual butterfly-shaped ion, SP(P2)PS, which can be visualised as a P4 molecule where two P−S bonds replace one P−P bond.[15] - P
7S3−
3 is a sulfido heptaphosphane cluster anion.[8]
References
- ^
- .
- PMID 7544885.
- .
- ^ R. Klement "Phosphorus" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1., p. 571.
- .
- ^ ISBN 978-0-08-022057-4.
- ^ ISBN 978-1-4398-4088-7
- PMID 11720507.
- ^ ISBN 0-12-352651-5
- ISSN 0044-2313.
- ISSN 0044-2313.
- ISSN 1042-6507.
- PMID 19621885.