Phosphorus triiodide

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Phosphorus triiodide
Phosphorus-triiodide-2D-dimensions.png
Phosphorus-triiodide-3D-vdW.png
PI3.jpg
Names
IUPAC names
Phosphorus triiodide
Phosphorus(III) iodide
Other names
Triiodophosphine
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.302 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-647-2
PubChem CID
UNII
  • InChI=1S/I3P/c1-4(2)3 Yes check.svgY
    Key: PZHNNJXWQYFUTD-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/I3P/c1-4(2)3
    Key: PZHNNJXWQYFUTD-UHFFFAOYAR
  • IP(I)I
Properties
PI3
Molar mass 411.68717 g/mol
Appearancedark red solid
Density 4.18 g/cm3
Melting point 61.2 °C (142.2 °F; 334.3 K)
Boiling point 200 °C (392 °F; 473 K) (decomposes)
Decomposes
Structure
Trigonal pyramidal
Hazards
GHS labelling: [1]
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H314, H335
P260, P280, P301+P330+P331, P303+P361+P353, P305+P351+P338
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
3
0
2
W
Flash point non-flammable
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Phosphorus triiodide (PI3) is an inorganic compound with the formula PI3. A red solid, it is [2] too unstable to be stored for long periods of time; 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.

Contents

Properties

Although PI3 is a pyramidal molecule, it has only a small molecular dipole because each P-I bond has almost no bond dipole moment. The P-I bond is also weak; PI3 is much less stable than PBr3 and PCl3, with a standard enthalpy of formation for PI3 of only −46 kJ/ mol (solid). The phosphorus atom has an NMR chemical shift of 178 ppm (downfield of H3PO4).

Reactions

Phosphorus triiodide reacts vigorously with water, producing phosphorous acid (H3PO3) and hydroiodic acid (HI), along with smaller amounts of phosphine and various P-P-containing compounds. Alcohols likewise form alkyl iodides, this providing the main use for PI3.

PI3 is also a powerful reducing agent and deoxygenating agent. It reduces sulfoxides to sulfides, even at −78 °C. [3] Meanwhile, heating a 1-iodobutane solution of PI3 with red phosphorus causes reduction to P2I4.

Preparation

The usual method or preparation is by the union of the elements, often by addition of iodine to a solution of white phosphorus in carbon disulfide:

P4 + 6 I2 → 4 PI3

Alternatively, PCl3 may be converted to PI3 by the action of hydrogen iodide or certain metal iodides.

Uses

Phosphorus triiodide is commonly used in the laboratory for the conversion of primary or secondary alcohols to alkyl iodides. [4] The alcohol is frequently used as the solvent, on top of being the reactant. Often the PI3 is made in situ by the reaction of red phosphorus with iodine in the presence of the alcohol; for example, the conversion of methanol to give iodomethane: [5]

PI3 + 3 CH
3
OH
→ 3 CH
3
I
+ " H
3
PO
3
"

These alkyl iodides are useful compounds for nucleophilic substitution reactions, and for the preparation of Grignard reagents.

See also

Related Research Articles

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

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

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

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<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">Hydrogen iodide</span> Chemical compound

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3
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<span class="mw-page-title-main">Thiophosphoryl chloride</span> Chemical compound

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<span class="mw-page-title-main">Sulfenyl chloride</span> Chemical group (R–S–Cl)

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<span class="mw-page-title-main">Reductions with samarium(II) iodide</span>

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References

  1. GHS: Sigma-Aldsrich 241555
  2. L. G. Wade, Jr., Organic Chemistry, 6th ed., p. 477, Pearson/Prentice Hall, Upper Saddle River, New Jersey, USA, 2005.
  3. J. N. Denis; A. Krief (1980). "Phosphorus tri-iodide (PI3), a powerful deoxygenating agent". J. Chem. Soc., Chem. Commun. (12): 544–5. doi:10.1039/C39800000544.
  4. B. S. Furnell et al., Vogel's Textbook of Practical Organic Chemistry, 5th edition, Longman/Wiley, New York, 1989.
  5. King, C. S.; Hartman, W. W. (1933). "Methyl Iodide". Organic Syntheses . 13: 60. doi:10.15227/orgsyn.013.0060.