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. [1] Mixed chalcogen halides also exist.
Chemical formula | CAS number | Melting point | Boiling point | P–Xax bond length | P–Xeq bond length | Xeq–P–Xeq bond angle | Xax–P–Xeq bond angle |
---|---|---|---|---|---|---|---|
PF5 Phosphorus pentafluoride | [7647-19-0] | -93.7°C | -84.5°C | 153 pm | 158 pm | 120° | 90° |
PCl5 Phosphorus pentachloride | [10026-13-8] | 160°C | 167°C | 214 pm | 202 pm | 120° | 90° |
PBr5 Phosphorus pentabromide | [7789-69-7] | ~106°C d | |||||
PBr7 Phosphorus heptabromide | [14337-11-2] | ||||||
PI5 Phosphorus pentaiodide | See Tornieporth-Getting & Klapötke 1990 |
In the gas phase the phosphorus pentahalides have trigonal bipyramidal molecular geometry as explained by VSEPR theory.
Phosphorus pentafluoride is a relatively inert gas, notable as a mild Lewis acid and a fluoride ion acceptor. It is a fluxional molecule in which the axial (ax) and equatorial (eq) fluorine atoms interchange positions by the Berry pseudorotation mechanism.
Phosphorus pentachloride, phosphorus pentabromide, and phosphorus heptabromide are ionic in the solid and liquid states; PCl5 is formulated as PCl4+PCl6–, but in contrast, PBr5 is formulated as PBr4+ Br−, and PBr7 is formulated as PBr4+ Br3−. They are widely used as chlorinating and brominating agents in organic chemistry.
Chemical formula | CAS number | Melting point | Boiling point | P–X bond length | X–P–X bond angle | Dipole moment |
---|---|---|---|---|---|---|
PF3 Phosphorus trifluoride | [7783-55-3] | -151.5°C | -101.8°C | 156 pm | 96.3° | 1.03 D |
PCl3 Phosphorus trichloride | [7719-12-2] | -93.6°C | 76.1°C | 204 pm | 100° | 0.56 D |
PBr3 Phosphorus tribromide | [7789-60-8] | -41.5°C | 173.2°C | 222 pm | 101° | |
PI3 Phosphorus triiodide | [13455-01-1] | 61.2°C | 227°C | 243 pm | 102° | |
P(CN)3 Phosphorus tricyanide [2] | 203°C | 179 pm |
The phosphorus(III) halides are the best known of the three series. They are usually prepared by direct reaction of the elements, or by transhalogenation.
Phosphorus trifluoride is used as a ligand in coordination chemistry, where it resembles carbon monoxide. Phosphorus trichloride is a major industrial chemical and widely used starting material for phosphorus chemistry. Phosphorus tribromide is used in organic chemistry to convert alcohols to alkyl bromides and carboxylic acids to acyl bromides (e.g. in the Hell-Volhard-Zelinsky reaction). Phosphorus triiodide also finds use in organic chemistry, as a mild oxygen acceptor.
The trihalides are fairly readily oxidized by chalcogens to give the corresponding oxyhalides or equivalents.
Chemical formula | CAS number | Melting point | Boiling point | P–X bond length | P–P bond length | X–P–X bond angle | X–P–P bond angle |
---|---|---|---|---|---|---|---|
P2F4 Diphosphorus tetrafluoride | [13824-74-3] | -86.5°C | -6.2°C | 159 pm | 228 pm | 99.1° | 98.4° |
P2Cl4 Diphosphorus tetrachloride | [13467-91-1] | -28°C | ~180°C d | ||||
P2Br4 Diphosphorus tetrabromide | [24856-99-3] | poorly characterized | |||||
P2I4 Diphosphorus tetraiodide | [13455-00-0] | 125.5°C | d | 248 pm | 221 pm | 102.3° | 94.0° |
Phosphorus(II) halides may be prepared by passing an electric discharge through a mixture of the trihalide vapour and hydrogen gas.[ citation needed ] The relatively stable P2I4 is known to have a trans, bent configuration similar to hydrazine and finds some uses in organic syntheses, the others are of purely academic interest at the present time. Diphosphorus tetrabromide is particularly poorly described. They are subhalides of phosphorus.
Chemical formula | CAS number | EINECS number | Melting point | Boiling point | Density | Refractive index | Dipole moment |
---|---|---|---|---|---|---|---|
POF3 Phosphorus oxyfluoride | [13478-20-1] | ? | −39.1°C | −39.7°C | 0,003596 g/cm3 | ? | ? |
POCl3 Phosphorus oxychloride | [10025-87-3] | 233-046-7 | 1.2°C | 105.1°C | 1.675 g/cm3 | 1.461 | 2.54 D |
POBr3 Phosphorus oxybromide | [7785-59-5] | 232-177-7 | 56°C | 192°C | 2.82 g/cm3 | ? | ? |
POI3 Phosphorus oxyiodide | [13455-04-4] | ? | 53°C | – | ? | ? | ? |
PSF3 Thiophosphoryl fluoride | [2404-52-6] | ? | −148.8°C | −52.2°C | 1.56 g/cm3(l) | 1.353 | ? |
PSCl3 Thiophosphoryl chloride | [3982-91-0] | 223-622-6 | -35°C | 125°C | 1.668 g/cm3 | 1.555 | ? |
PSBr3 Thiophosphoryl bromide | [3931-89-3] | ? | 37.8°C | 212°C decomp | ? | ? | ? |
PSI3 Thiophosphoryl iodide | [63972-04-3] | ? | 48°C | decomp | ? | ? | ? |
PSeF3 Selenophosphoryl fluoride Phosphoroselenoic trifluoride | [26083-30-7] | ? | ? | ? | ? | ? | ? |
PSeCl3 Selenophosphoryl chloride Phosphoroselenoic trichloride | [63944-06-9] | ? | ? | ? | ? | ? | ? |
PSeBr3 Selenophosphoryl bromide | [62565-69-9] | ? | ? | ? | ? | ? | ? |
PSeI3 Selenophosphoryl iodide | [39383-15-8] | ? | ? | ? | ? | ? | ? |
The oxyhalides may be prepared from the corresponding trihalides by reaction with organic peroxides or ozone: they are sometimes referred to as phosphoryl halides.
The thiohalides, also known as thiophosphoryl halides may be prepared from the trihalides by reaction with elemental sulfur in an inert solvent. The corresponding selenohalides are also known.
The oxyhalides and thiohalides are significantly more electrophilic than the corresponding phosphorus(III) species, and present a significant toxic hazard.
The chalcogens are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the radioactive elements polonium (Po) and livermorium (Lv). Often, oxygen is treated separately from the other chalcogens, sometimes even excluded from the scope of the term "chalcogen" altogether, due to its very different chemical behavior from sulfur, selenium, tellurium, and polonium. The word "chalcogen" is derived from a combination of the Greek word khalkos (χαλκός) principally meaning copper, and the Latinized Greek word genēs, meaning born or produced.
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.
The pnictogens are the chemical elements in group 15 of the periodic table. This group is also known as the nitrogen group or nitrogen family. Group 15 consists of the elements nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and moscovium (Mc).
Hydrogen bromide is the inorganic compound with the formula HBr. It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temperature. Aqueous solutions that are 47.6% HBr by mass form a constant-boiling azeotrope mixture that boils at 124.3 °C (255.7 °F). Boiling less concentrated solutions releases H2O until the constant-boiling mixture composition is reached.
Phosphorus tribromide is a colourless liquid with the formula PBr3. The liquid fumes in moist air due to hydrolysis and has a penetrating odour. It is used in the laboratory for the conversion of alcohols to alkyl bromides.
Phosphorus pentabromide is a reactive, yellow solid of formula PBr5, which has the structure [PBr4]+Br− in the solid state but in the vapor phase is completely dissociated to PBr3 and Br2. Rapid cooling of this phase to 15 K leads to formation of the ionic species phosphorus heptabromide.
Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.
The Michaelis–Arbuzov reaction is the chemical reaction of a trivalent phosphorus ester with an alkyl halide to form a pentavalent phosphorus species and another alkyl halide. The picture below shows the most common types of substrates undergoing the Arbuzov reaction; phosphite esters (1) react to form phosphonates (2), phosphonites (3) react to form phosphinates (4) and phosphinites (5) react to form phosphine oxides (6).
Hydrogen iodide (HI) is a diatomic molecule and hydrogen halide. Aqueous solutions of HI are known as hydroiodic acid or hydriodic acid, a strong acid. Hydrogen iodide and hydroiodic acid are, however, different in that the former is a gas under standard conditions, whereas the other is an aqueous solution of the gas. They are interconvertible. HI is used in organic and inorganic synthesis as one of the primary sources of iodine and as a reducing agent.
Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive towards water.
Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.
Gold(III) bromide is a dark-red to black crystalline solid. It has the empirical formula AuBr3, but exists as a dimer with the molecular formula Au2Br6 in which two gold atoms are bridged by two bromine atoms. It is commonly referred to as gold(III) bromide, gold tribromide, and rarely but traditionally auric bromide, and sometimes as digold hexabromide. The analogous copper or silver tribromides do not exist.
Gallium(III) bromide (GaBr3) is a chemical compound, and one of four gallium trihalides.
Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X− couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.
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.
Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.
Einsteinium compounds are compounds that contain the element einsteinium (Es). These compounds largely have einsteinium in the +3 oxidation state, or in some cases in the +2 and +4 oxidation states. Although einsteinium is relatively stable, with half-lives ranging from 20 days upwards, these compounds have not been studied in great detail.
Zirconium(III) bromide is an inorganic compound with the formula ZrBr3.
Gallium compounds are compounds containing the element gallium. These compounds are found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C, disproportionating into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the dioxan complex Ga2Cl4(C4H8O2)2. There are also compounds of gallium with negative oxidation states, ranging from -5 to -1, most of these compounds being magnesium gallides (MgxGay).
Thiophosphoryl bromide is an inorganic compound with the formula PSBr3.