Boron trichloride

Boron trichloride
Identifiers
CAS number 10294-34-5 Y
PubChem 25135
ChemSpider 16788234 Y
EC number 233-658-4
RTECS number ED1925000
Jmol-3D images Image 1
Properties
Molecular formula BCl3
Molar mass 117.17 g/mol
Appearance Colorless gas,
fumes in air
Density 1.326 g/cm3
Melting point

-107.3 °C

Boiling point

12.6 °C [1]

Solubility in water decomp.
Solubility decomposes in ethanol
soluble in CCl4
Refractive index (nD) 1.00139
Structure
Molecular shape Trigonal planar (D3h)
Dipole moment zero
Hazards[2]
MSDS ICSC 0616
GHS pictograms
GHS signal word DANGER
GHS hazard statements H330, H300, H314 [note 1]
EU Index 005-002-00-5
EU classification Very toxic (T+)
Corrosive (C)
R-phrases R14, R26/28, R34
S-phrases (S1/2), S9, S26, S28,
S36/37/39, S45
NFPA 704
0
4
2
Flash point Non-flammable
Related compounds
Other anions Boron trifluoride
Boron tribromide
Boron triiodide
Other cations Aluminium chloride
Gallium chloride
Related compounds Boron trioxide
Carbon tetrachloride
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Boron trichloride is a chemical compound with the formula BCl3. This colorless gas is a valuable reagent in organic synthesis. It is also dangerously reactive.

Contents

Production and properties

Boron reacts with halogens to give the corresponding trihalides. Boron trichloride is, however, produced industrially by direct chlorination of boron oxide and carbon at 500 °C.

B2O3 + 3 C + 3 Cl2 → 2 BCl3 + 3 CO

The synthesis is analogous to the Kroll process for the conversion of titanium dioxide to titanium tetrachloride. In the laboratory BF3 reacted with AlCl3 gives BCl3 via halogen exchange.[3] BCl3 is a trigonal planar molecule like the other boron trihalides, and has a bond length of 175pm. It has a zero dipole moment because it is symmetric and therefore the dipole moments associated with the bonds cancel each other out. Boron trichloride does not form dimers, although there is some evidence that may indicate dimerisation at very low temperatures (20 K). NMR studies of mixtures of boron trihalides shows the presence of mixed halides which may indicate a four centre intermediate e.g. a dimer. The absence of dimerisation contrasts with the other trihalides of group 13 which contain 4 or 6 coordinate metal centres, for example see AlCl3 and GaCl3. A degree of π-bonding has been proposed to explain the short B− Cl distance although there is some debate as to its extent.[3]

BCl3 is a Lewis acid readily forming adducts with tertiary amines, phosphines, ethers, thioethers, and halide ions.[4] For example, BCl3S(CH3)2 (CAS# 5523-19-3) is often employed as a conveniently handled source of BCl3 because this solid (m.p. 88-90 °C) releases BCl3:

(CH3)2SBCl3 ⇌ (CH3)2S + BCl3

When boron trichloride is passed at low pressure through devices delivering an electric discharge, diboron tetrachloride,[5] Cl2B-BCl2, and tetraboron tetrachloride, formula B4Cl4, are formed. Colourless diboron tetrachloride (m.p. -93 °C) has a planar molecule in the solid, (similar to dinitrogen tetroxide, but in the gas phase the structure is staggered[3]. It decomposes at room temperatures to give a series of monochlorides having the general formula (BCl)n, in which n may be 8, 9, 10, or 11; the compounds with formulas B8Cl8 and B9Cl9 are known to contain closed cages of boron atoms.

The mixed aryl and alkyl boron chlorides are also of interest. Phenylboron dichloride is commercially available. Such species can be prepared by the reaction of BCl3 with organotin reagents:

2 BCl3 + R4Sn → 2 RBCl2 + R2SnCl2

Uses

Boron trichloride is a starting material for the production of elemental boron. It is also used in the refining of aluminium, magnesium, zinc, and copper alloys to remove nitrides, carbides, and oxides from molten metal. It has been used as a soldering flux for alloys of aluminium, iron, zinc, tungsten, and monel. Aluminum castings can be improved by treating the melt with boron trichloride vapors. In the manufacture of electrical resistors, a uniform and lasting adhesive carbon film can be put over a ceramic base using BCl3. It has been used in the field of high energy fuels and rocket propellants as a source of boron to raise BTU value. BCl3 is also used in plasma etching in semiconductor manufacturing. This gas etches metal oxides by formation of a volatile BOClx compounds.

BCl3 is used as a reagent in the synthesis of organic compounds. Like the corresponding bromide, it cleaves C-O bonds in ethers.[6]

Safety

BCl3 is an aggressive reagent that releases hydrogen chloride upon exposure to moisture or alcohols. The dimethyl sulfide adduct is safer to use, when possible.

References

  1. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0070494398
  2. ^ Index no. 005-002-00-5 of Annex VI, Part 3, to Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006. OJEU L353, 31.12.2008, pp 1–1355 at p 341.
  3. ^ a b c Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. ISBN 0080379419. 
  4. ^ W. Gerrard and M. F. Lappert (1958). "Reactions Of Boron Trichloride With Organic Compounds". Chemical Reviews 58 (6): 1081–1111. doi:10.1021/cr50024a003. 
  5. ^ Wartik, T.; Rosenberg, R.; Fox, W. B. "Diboron tetrachloride" Inorganic Syntheses 1967, volume X, pages 118-126.
  6. ^ Yamamoto, Y.; Miyaura, N. "Boron Trichloride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
  1. ^ Within the European Union, the following additional hazard statement (EUH014) must also be displayed on labelling: Reacts violently with water.

See also

Further reading

External links