Encyclopedia
Diborane is the chemical compound with the formula B
2H
6. It is a colorless gas at room temperature with a repulsively sweet odor. B
2H
6 mixes well with air, easily forming explosive mixtures. Diborane will ignite spontaneously in moist air at room temperature. Synonyms include boroethane, boron hydride, and diboron hexahydride . B
2H
6 is a key boron compound with a variety of applications. The compound is endothermic as indicated by a positive heat of formation, ?H°
f of 36 kJ/mol. Despite its intrinsic instability, B
2H
6 is kinetically quite stable and enjoys an extensive chemistry.
Structure and bonding
Diborane adopts a C
2v structure containing four terminal and two bridging hydrides. The
molecular orbital model indicates that the bonding between boron and the terminal hydrides is fairly conventional, not unlike the bonding between carbon and hydride in ethane. The bonding between the boron atoms and the bridging hydrogen atoms is, however, distinctive relative to ordinary hydrocarbons. Formed two 2-center, 2-electron bonds with the terminal hydrogen atoms, each boron "has" one electron remaining for additional bonding. The bridging hydrogen atoms each provide one electron each. Thus the B
2H
2 ring is held together with four electrons. The lengths of the B-H
bridge bonds and the B-H
terminal bonds are 1.33 and 1.19 Å, respectively. The difference in the lengths of these bonds reflects the difference in their strengths: the B-H
bridge bonds are relatively weaker. The bonding between the boron atoms and two bridging hydrides of diborane is an example of 3-center-2-electron bonding. The structure is equivalent to that for isoelectronic [C
2H
62+, which would arise from the diprotonation of the planar molecule
ethene. B
2H
6 is one of many compounds with such unusual bonding.
Production and syntheses
Diborane is so central and has been studied so often that many syntheses exist. Most preparations entail reactions of hydride donors with boron halides or alkoxides. The industrial synthesis involves the reduction of BF
3:
- 2 BF3 + 6 NaH ? B2H6 + 6 NaF
...
Two laboratory methods start from
boron trichloride with
lithium aluminium hydride or from
boron trifluoride ether solution with
sodium borohydride. Both methods yield in up to 30% of diborane:
- 4 BCl3 + 3 LiAlH4 ? 2 B2H6 + 3 LiAlCl4
- 4 BF3 + 3 NaBH4 ? 2 B2H6 + 3 NaBF4
Older methods entail the direct reaction of borohydride salts with a non-oxidizing acid, such as
sulfuric acid or
phosphoric acid.
- 2 BH4- + 2 H+ ? 2H2 + B2H6
Similarly, oxidation of borohydride salts has been demonstrated and remains convenient for small scale preparations:
- 2 NaBH4 + I2 ? 2 NaI + B2H6 + H2
| Triple point [i] || 13.8033 K, 7.042 kPa
...
Reactions
Diborane is a highly reactive and versatile reagent that has a large number of applications. Its dominating reaction pattern involves formation of adducts with Lewis bases. Often such initial adducts proceed rapidly to give other products. It reacts with
ammonia to form
borazine. Diborane also reacts readily with
alkynes to form substituted
alkene products which will readily undergo further addition reactions.
Diborane reacts with water to form hydrogen and
boric acid.
The compound forms complexes with Lewis bases. Notable are the complexes with
THF and
dimethyl sulfide, both liquid compounds are popular reducing agents in
organic chemistry. In these 1:1 complexes, boron assumes a tetrahedral geometry, being bound to three hydrides and the Lewis base . The THF adduct is usually prepared as a 1:5 solution in THF. The latter is indefinitely stable when stored under nitrogen at room temperature.
Reagent in organic synthesis
Diborane is the central reagent for
hydroboration, whereby alkenes add across the B-H bonds to give trialkylboranes:
- BH3 + 3 CH2=CHR ? B3 + THF
This reaction is regioselective, and the product trialkylboranes can be converted to useful organic derivatives. With bulky alkenes one can prepare species such as [HBR
2]
2, which are also useful reagents in more specialized applications.
Diborane is used as a reducing agent roughly complementary to the reactivity of
lithium aluminium hydride. The compound readily reduces
carboxylic acids to the corresponding
alcohols, whereas
ketones react only sluggishly.
History
Diborane was first synthesised in the 19 century by pyrolysis of metal borides, but it was never analyzed. From 1912 to 1936, the major pioneer in the chemistry of boron hydrides, Alfred Stock, undertook his research that led to the methods for the synthesis and handling of the highly reactive, volatile, and often toxic boron hydrides. He proposed the first ethane like structure of diborane.
Electron diffraction from H. Bauer appeared to initially supported his proposed structure.
Despite a personal communication with
Pauling, Schlesinger he did not specifically discuss 3-center-2-electron bonding in his then classic review in the early 1940's. The review does, however, discuss the C
2v structure in some depth, "It is to be recognized that this formulation easily accounts for many of the chemical properties of diborane..."
In 1943 an undergraduate student, H. Christopher Longuet-Higgins, in Oxford published the currently accepted structure together with R. P. Bell,. This structure had already been described in 1921. The years following the Longuet-Higgins/Bell proposal witnessed a colorful discussion about the correct structure. The debate ended with the electron diffraction measurement in 1951 by K. Hedberg and V. Schomaker, with the confirmation of the structure shown in the schemes on this page.
William Nunn Lipscomb, Jr. further confirmed the molecular structure of boranes using
X-ray crystallography in the 1950's, and developed theories to explain its bonding. Later, he applied the same methods to related problems, including the structure of carboranes on which he directed the research of future
Nobel Prize winner Roald Hoffmann. Lipscomb received The
Nobel Prize in Chemistry in 1976 for his efforts.
Other uses
Diborane is used in rocket propellants, as a
rubber vulcanizer, as a
catalyst for
hydrocarbon polymerization, as a flame-speed accelerator, and as a doping agent for the production of semiconductors. It is also an intermediate in the production of highly pure
boron for semiconductor production.
Safety
The toxic effects of diborane are primarily due to its irritant properties. Short-term exposure to diborane can cause a sensation of tightness of the chest, shortness of breath, cough, and wheezing. These signs and symptoms can occur immediately or be delayed for up to 24 hours. Skin and eye irritation can also occur. Studies in animals have shown that diborane causes the same type of effects observed in humans.
People exposed for a long time to low amounts of diborane have experienced respiratory irritation, seizures, fatigue, drowsiness, confusion, and occasional transient tremors.
References
Further reading
H. C. Brown "Organic Synthesis via Boranes" John Wiley, New York, 1975. ISBN 0-471-11280-1.
External links
