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Tributylphosphine

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Tributylphosphine
Names
IUPAC name Tributylphosphane
Other names Tributylphosphine
Identifiers
CAS Number
3D model (JSmol)
ECHA InfoCard 100.012.410 Edit this at Wikidata
EC Number
  • 213-651-2
CompTox Dashboard (EPA)
InChI
  • InChI=1/C12H27P/c1-4-7-10-13(11-8-5-2)12-9-6-3/h4-12H2,1-3H3
SMILES
  • CCCCP(CCCC)CCCC
Properties
Chemical formula C
12H
27P
Molar mass 204.25 g/mol
Appearance Colorless oily liquid
Density 0.82 g/ml
Melting point −60 °C; −76 °F; 213 K
Boiling point 240 °C; 464 °F; 513 K
Solubility in water negligible
Dipole moment ?
Hazards
Occupational safety and health (OHS/OSH):
Main hazards Stench, Flammable, Corrosive
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 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 hazards (white): no code
1 3 2
Flash point 117 °C
Supplementary data page
]
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Tributylphosphine, formula P(C
4H
9)
3 or PBu
3, is a tertiary phosphine, most commonly encountered as a ligand in transition metal complexes. It is an oily liquid at room temperature, with a nauseating odor. It reacts slowly with atmospheric oxygen, and rapidly with other oxidizing agents, to give the corresponding phosphine oxide. It is usually handled using air-free techniques.

Preparation

Tributylphosphine is prepared industrially by the addition of phosphine to butene: the addition proceeds by a free radical mechanism, and so the Markovnikov rule is not followed.

PH
3 + 3CH
2=CHCH
2CH
3 → P(CH
2CH
2CH
2CH
3)
3

Tributylphosphine can be prepared in the laboratory by reaction of the appropriate Grignard reagent with phosphorus trichloride although, as it is commercially available at reasonable prices, it is rare to have to perform the small-scale preparation.

3BuMgCl + PCl
3 → PBu
3 + 3MgCl
2

Use

Tributylphosphine finds some industrial use as a catalyst modifier in the cobalt-catalyzed hydroformylation of alkenes, where it greatly increases the ratio of straight-chain aldehydes to branched-chain aldehydes in the product mixture. However, tricyclohexylphosphine is even more effective for this purpose (although more expensive) and, in any case, rhodium catalysts are usually preferred to cobalt catalysts for the hydroformylation of alkenes.

Tributylphosphine is also a common ligand for the preparation of complexes of transition metals in relatively low oxidation states, as it is cheap and less air-sensitive. It has a conveniently low volatility, which makes it easier to handle than other trialkylphosphines. Although its complexes are generally highly soluble, they are often more difficult to crystallize compared to complexes of more rigid phosphines. Furthermore, the 1H NMR properties are less easily interpreted and can mask signals for other ligands. Compared to other tertiary phosphines, it is compact (cone angle: 136°) and basic (χ-parameter: 5.25 cm)

Hazards

The main laboratory inconvenience of tributylphosphine is its extremely strong and unpleasant smell. All manipulations must be carried out in an efficient fume hood, and glassware which has come into contact with the compound must be decontaminated before leaving the hood. Because tributylphosphine must be protected from the atmosphere, it is usually handled using syringe techniques. The manipulation of large quantities requires specific precautions to prevent the release of the vapour into the environment. For transport purposes, it is classified as a "spontaneously flammable liquid" (group 4.2), although this is rarely a significant problem in the laboratory use of small quantities: it may not be transported by air.

References

  1. Tributylphosphine is the most widely used name for this compound. However Iupac nomenclature prefers the name tributylphosphane, which is also the U.S. proper shipping name (49 CFR 172.101).
  2. Bell, P. (1968). "Zur Frage der Isomerenbildung bei der Hydroformylierung Höhermolekularer Olefine mit Komplexen Kobalt- und Rhodiumkatalysatoren". Tetrahedron Lett.: 3262–66. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  3. Rahman, M. M. (1987). "Steric and Electronic Factors influencing Transition-Metal–Phosphorus(III) Bonding". Organometallics. 6 (3): 650–58. doi:10.1021/om00146a037. {{cite journal}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
  4. 49 CFR 172.101.

External links

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