Thiophosphoryl bromide

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Thiophosphoryl bromide
Thiophosphoryl bromide.svg
Thiophosphoryl-bromide-GED-3D-sf.png
Names
Other names
Thiophosphoryl tribromide
Phosphorus thiobromide
Phosphorothioic tribromide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.021.367 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 223-502-3
PubChem CID
  • InChI=1S/Br3PS/c1-4(2,3)5
    Key: OWNZHTHZRZVKSQ-UHFFFAOYSA-N
  • S=P(Br)(Br)Br
Properties
PSBr3
Molar mass 302.75 g·mol−1
Appearanceyellow crystals [1] [2]
Density 2.85 g cm−3 [2]
Melting point 37.8 °C (100.0 °F; 310.9 K)
Boiling point 212 °C (414 °F; 485 K) decomposes [2]
Structure [3]
Cubic
Pa3, No. 205
a = 11.03 Å, b = 11.03 Å, c = 11.03 Å
Tetrahedral at the P atom
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Thiophosphoryl bromide is an inorganic compound with the formula P S Br 3. [1]

Contents

Preparation

Thiophosphoryl bromide can be prepared by heating phosphorus tribromide with phosphorus pentasulfide, or with elemental sulfur in an inert atmosphere at 130 °C. [4]

Thiophosphoryl bromide is one product of the bromination of P4S7 in cold carbon disulfide: [1]

3 P4S7 + 12 Br2 → 2 PBr3 + 2 PSBr3 + 2 P2S6Br2 + 2 P2S5Br4

Structure and properties

Thiophosphoryl bromide has tetrahedral molecular geometry and C3v molecular symmetry. According to gas electron diffraction, the phosphorus–sulfur bond length is 1.895 Å and the phosphorus–bromine bond length is 2.193 Å, while the S=P−Br bond angle is 116.2° and the Br−P−Br bond angle is 101.9°. [5]

Thiophosphoryl bromide is soluble in carbon disulfide, chloroform and diethyl ether. [4]

Reactions

Like other phosphoryl and thiophosphoryl halides, [1] thiophosphoryl bromide readily hydrolyses, undergoes nucleophilic substitution and forms adducts with Lewis acids. [6] Reaction with lithium iodide generates the mixed thiophosphoryl halides PSBr2I and PSBrI2 but not thiophosphoryl iodide, PSI3. [7] Thiophosphoryl bromide is of use in organic synthesis for reducing sulfoxides to thioethers, [8] and sulfines to thioketones. [9]

Related Research Articles

<span class="mw-page-title-main">Bromine</span> Chemical element, symbol Br and atomic number 35

Bromine is a chemical element with the symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig and Antoine Jérôme Balard, its name was derived from the Ancient Greek βρῶμος (bromos) meaning "stench", referring to its sharp and pungent smell.

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

<span class="mw-page-title-main">Phosphonium</span> Family of polyatomic cations containing phosphorus

In chemistry, the term phosphonium describes polyatomic cations with the chemical formula PR+
4
. These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Phosphorus triiodide</span> Chemical compound

Phosphorus triiodide (PI3) is an inorganic compound with the formula PI3. A red solid, it is too unstable to be stored; it is, nevertheless, commercially available. It is widely used in organic chemistry for converting alcohols to alkyl iodides. It is also a powerful reducing agent. Note that phosphorus also forms a lower iodide, P2I4, but the existence of PI5 is doubtful at room temperature.

In chemistry, there are three series of binary phosphorus halides, containing phosphorus in the oxidation states +5, +3 and +2. All compounds have been described, in varying degrees of detail, although serious doubts have been cast on the existence of PI5. Mixed chalcogen halides also exist.

<span class="mw-page-title-main">Copper(I) iodide</span> Chemical compound

Copper(I) iodide is the inorganic compound with the formula CuI. It is also known as cuprous iodide. It is useful in a variety of applications ranging from organic synthesis to cloud seeding.

<span class="mw-page-title-main">Phosphorus pentasulfide</span> Chemical compound

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 (empirical) or P4S10 (molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.

<span class="mw-page-title-main">Aluminium iodide</span> Chemical compound

Aluminium iodide is a chemical compound containing aluminium and iodine. Invariably, the name refers to a compound of the composition AlI
3
, formed by the reaction of aluminium and iodine or the action of HI on Al metal. The hexahydrate is obtained from a reaction between metallic aluminum or aluminum hydroxide with hydrogen iodide or hydroiodic acid. Like the related chloride and bromide, AlI
3
is a strong Lewis acid and will absorb water from the atmosphere. It is employed as a reagent for the scission of certain kinds of C-O and N-O bonds. It cleaves aryl ethers and deoxygenates epoxides.

Tin(II) bromide is a chemical compound of tin and bromine with a chemical formula of SnBr2. Tin is in the +2 oxidation state. The stability of tin compounds in this oxidation state is attributed to the inert pair effect.

<span class="mw-page-title-main">Selenium compounds</span> Chemical compounds containing selenium

Selenium compounds commonly exist in the oxidation states −2, +2, +4, and +6.

Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.

In inorganic chemistry, sulfonyl halide groups occur when a sulfonyl functional group is singly bonded to a halogen atom. They have the general formula RSO2X, where X is a halogen. The stability of sulfonyl halides decreases in the order fluorides > chlorides > bromides > iodides, all four types being well known. The sulfonyl chlorides and fluorides are of dominant importance in this series.

There are three sets of Indium halides, the trihalides, the monohalides, and several intermediate halides. In the monohalides the oxidation state of indium is +1 and their proper names are indium(I) fluoride, indium(I) chloride, indium(I) bromide and indium(I) iodide.

<span class="mw-page-title-main">Thiophosphoryl chloride</span> Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

<span class="mw-page-title-main">Diphosphorus tetraiodide</span> Chemical compound

Diphosphorus tetraiodide is an orange crystalline solid with the formula P2I4. It has been used as a reducing agent in organic chemistry. It is a rare example of a compound with phosphorus in the +2 oxidation state, and can be classified as a subhalide of phosphorus. It is the most stable of the diphosphorus tetrahalides.

<span class="mw-page-title-main">Thiophosphoryl fluoride</span> Chemical compound

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

<span class="mw-page-title-main">Sulfinyl halide</span> Class of chemical compounds

Sulfinyl halide have the general formula R−S(O)−X, where X is a halogen. They are intermediate in oxidation level between sulfenyl halides, R−S−X, and sulfonyl halides, R−SO2−X. The best known examples are sulfinyl chlorides, thermolabile, moisture-sensitive compounds, which are useful intermediates for preparation of other sufinyl derivatives such as sulfinamides, sulfinates, sulfoxides, and thiosulfinates. Unlike the sulfur atom in sulfonyl halides and sulfenyl halides, the sulfur atom in sulfinyl halides is chiral, as shown for methanesulfinyl chloride.

<span class="mw-page-title-main">Thiophosphoryl iodide</span> Chemical compound

Thiophosphoryl iodide is an inorganic compound with the formula PSI3.

<span class="mw-page-title-main">Tungsten hexabromide</span> Chemical compound

Tungsten hexabromide, also known as tungsten(VI) bromide, is a chemical compound of tungsten and bromine with the formula WBr6. It is an air-sensitive dark grey powder that decomposes above 200 °C to tungsten(V) bromide and bromine.

References

  1. 1 2 3 4 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 501–503. ISBN   978-0-08-037941-8.
  2. 1 2 3 William M. Haynes, ed. (2016). CRC Handbook of Chemistry and Physics (97th ed.). CRC Press. p. 4-78. ISBN   978-1498754293.
  3. "ICSD Entry: 39130". Cambridge Structural Database: Access Structures. Cambridge Crystallographic Data Centre. Retrieved 2022-10-30.
  4. 1 2 Arthur D. F. Toy (1975). The Chemistry of Phosphorus. Permanon Texts in Inorganic Chemistry. Vol. 3. Permanon Press. p. 438. ISBN   9781483139593.
  5. Jacob, E. Jean; Danielson, Donald D.; Samdal, Svein (1980). "An electron diffraction determination of the molecular structures of phosphoryl bromide and thiophosphoryl bromide". J. Mol. Struct. 62 (2): 143–155. Bibcode:1980JMoSt..62..143J. doi:10.1016/0022-2860(80)85232-X.
  6. van der Veer, W.; Jellinek, F. (1970). "Adducts of thiophosphoryl compounds with metal halides. Part III: Addition compounds of phosphoryl bromide and thiophosphoryl bromide". Recl. Trav. Chim. Pays-Bas . 89 (8): 833–844. doi:10.1002/recl.19700890809.
  7. Dillon, K. B.; Craveirinha Dillon, M. G.; Waddington, T. C. (1977). "The identification of some new thiophosphoryl compounds containing P–I bonds by means of 31P N.M.R. spectroscopy". Inorg. Nucl. Chem. Lett. 13 (8): 349–353. doi:10.1016/0020-1650(77)80109-8.
  8. Still, I. W. J.; Reed, J. N.; Turnbull, K. (1979). "Thiophosphoryl bromide: a new reagent for the reduction of sulfoxides to sulfides". Tetrahedron Lett. 20 (17): 1481–1484. doi:10.1016/S0040-4039(01)86183-9.
  9. Kuipers, J. A. M.; Lammerink, B. H. M.; Still, I . W. J.; Zwanenburg, B. (1981). "Phosphorus Pentasulfide and Thiophosphoryl Bromide: Facile Reagents for the Reduction of Sulfines to Thiones". Synthesis. 1981 (4): 295–297. doi:10.1055/s-1981-29423.