BORIDES

Boron forms one or more borides when it reacts with most metals. For
example, the reaction between magnesium and boron produces magnesium
boride, Mg3B2 .
3 Mg + 2 B → Mg3B2

This product reacts with acids to produce diborane, B2H6 .

Mg3B2 + 6 H+ → B2H6 + 3 Mg2+

Some metals react with boron to form borides containing the hexaboride
group, B62- . An example of this type of compound is calcium hexaboride,
CaB6 . In general, the structures of compounds of this type contain octahedral
B62- ions in a cubic lattice with metal ions. Most hexaborides are refractory
materials having melting points over 2000 °C.
 Boron Halides
As has already been mentioned, boron halides are electron-deficient molecules.
As a result, they tend to act as strong Lewis acids by accepting electron pairs
from many types of Lewis bases to form stable acid-base adducts.
2 B + 3 X2 → 2 BX3
2 B + 3 F2 → 2 BF3
2 B + 3 Cl2 → 2 BCl3
2 B + 3 Br2 → 2 BBr3

Because they are Lewis acids, boron halides also form complexes of the type
BX4ˉ . For example,
MCl + BCl3 → M+BCl4ˉ
The BX4ˉ ions are tetrahedral since the addition of the fourth Xˉ means that an
additional pair of electrons must be accommodated around the boron atom.
 Boron Halides
In addition to functioning as Lewis acids, boron halides undergo many other types of
reactions. As is typical of most compounds containing covalent bonds between a nonmetal
and a halogen, the boron halides react vigorously with water to yield boric acid and the
corresponding hydrogenhalide.
BX3 + 3 H2O → H3BO3 + 3 HX
The BX 3 compounds will also react with other protic solvents such as alcohols to yield
borate esters.
BX3 + 3 ROH → B(OR)3 + 3 HX
An unusual type of product known as a borazine is produced by the reaction of BCl 3 with
NH4Cl.
3 NH4Cl + 3 BCl3 → B3N3H3Cl 3 + 9 HCl
trichloroborazine
Diboron tetrahalides, B2X4 , are also known. These may be prepared in a variety of ways,
among them the reaction of BCl3 with mercury.

2 BCl3 + Hg Hg arc
B 2Cl 4 + Hg 2Cl2
 Boron Hydrides
There are many compounds that contain boron and hydrogen, and they are known
collectively as the boron hydrides . Six boron hydrides were prepared by Alfred
Stock in 1910–1930 by the addition of hydrochloric acid to magnesium boride that was
produced in small amounts when B2O3 was reduced with magnesium.

6 HCl + Mg 3B 2 → 3 MgCl 2 + B 2H6

Because of the extreme reactivity of boron hydrides (some are spontaneously fl ammable
in air), Stock developed procedures for handling such air-sensitive materials. The six
hydrides produced by Stock were B2H6, B4H10 , B5H9 , B5H11 , B6H10 , and B10H14 , with the
most interesting being diborane, B2H6.

The boron hydrides will all burn readily to produce B2O3 and water,
B2 H 6 + 3 O 2 → B2 O 3 + 3 H 2 O
 Boron Hydrides

Diborane undergoes is one in which it reacts with double bonds in hydrocarbons.

The reaction can be shown as

B2H6 + 6 RCH=CH2 → 2 B(CH2CH2R)3

This type of reaction is known as hydroboration , and it was exploited by H. C.

Brown as a route to organic derivatives of the boranes.
 Polyhedral Boranes
In a large number of compounds containing boron and hydrogen, the boron atoms are
arranged in the form of a well-defined polyhedron (octahedron, square antiprism, bicapped
square antiprism, icosahedron, etc.). In these structures, the boron atoms are most often
bonded to four, fi ve, or six other atoms. The most common structure is the icosahedron
exhibited by the species B12H122- . This structure consists of a B12 icosahedron with a
hydrogen atom bonded to each boron atom and the overall structure having a -2 charge. It
is prepared by the reaction of B2H6 with a base, which aids in the removal of hydrogen.

6 B2H6 + 2 (CH3)3 N [(CH3)3 NH+ ]2 B12H12 + 11 H2

150⁰C
Compounds such as Cs 2 B12H12 are stable to several hundred degrees and do not react as
reducing agents as does BH4ˉ . A large number of derivatives of B12H122- have been prepared
in which all or part of the hydrogen atoms are replaced by other groups such as Cl, F, Br,
NH2 , OH, CH3 , OCH3 ,COOH, etc.
 Polyhedral Boranes
The B9H92- ion has the structure shown in Figure 13.3 . Six of the boron atoms
form a trigonal prism, and the other three give a “ cap ” on each rectangular face
of the prism. The structure of the B6H62- ion is much simpler. It consists of an
octahedron of boron atoms with a B – H group at each apex.
 Polyhedral Boranes
Another anion containing boron and hydrogen is B10H102- . In the structure of this
ion, eight boron atoms form a square antiprism while the other two are located
above and below the square faces. The arrangement of boron atoms is shown in
Figure 13.4 . An enormous number of derivatives of these basic polyhedral units
(and also larger ones) exist, and a great deal of their chemistry is known.
 Polyhedral Boranes

In order to describe derivatives of B12 or B12H122- having icosahedral structures, it

is necessary to have a way to designate positions of atoms or substituent groups.
In order to do that, the positions are identified by a numbering system that is
illustrated as shown in Figure 13.5 .
 Boron Nitrides

♣ Because boron has three valence-shell electrons and nitrogen has five, the
molecule BN is isoelectronic with C2 .

♣ Also, some of the allotropic forms that exist for carbon (graphite and diamond)
also exist for materials that have the formula (BN)x .

♣ The form of (BN) x having the graphite structure is very similar to graphite in
many ways. Its structure consists of layers of hexagonal rings containing
alternating boronand nitrogen atoms. Unlike graphite, the layers of boron nitride
fall directly in line with one another rather than being staggered. The structure
of this form of boron nitride is shown in Figure 13.9 .
Structure of Boron Nitrides
Structure of Boron Nitrides and
graphite
 Boron Nitrides
♣ Under high pressure and temperature, boron nitride can be converted to a cubic
form. The cubic form of (BN)x is known as borazon , and it has a structure
similar to that of diamond.
♣ Boron also forms many other compounds with nitrogen. One of the most
interesting of these is borazine, B3N3H6 (m.p. 58°C, b.p. 54.5°C).
♣ Shown here is the structure of borazine, which is similar to the structure of
benzene. In fact, borazine has sometimes been referred to as “ inorganic benzene.
”
 Boron Nitrides

♣ When subjected to high temperature under vacuum, borazine loses hydrogen

and polymerizes to yield products known as biborazonyl and naphthazine ,
whose structures are similar to biphenyl and naphthalene, respectively.

♣ Although borazine resembles the aromatic benzene molecule in some respects,

the electronic structure is considerably different.

♣ Theoretical studies have shown that although there is some delocalization in

borazine, it is not as complete as in benzene.
 Boron Nitrides

Borazine was fi rst prepared in 1926 by the reaction of B2H6 with NH3 , which
can be shown as
B2H6 + 2 NH3 → 2 H3N˸BH3
200⁰C
2 H3N˸BH3 B3N3H6 + 6 H2

However, it can also be prepared by the following reactions:

C H Cl
6 5

3 NH4Cl + 3 BCl3 B3N3H3Cl3 + 9 HCl

140 – 150⁰C
6 NaBH4 + 2 B3N3H3Cl3 B3N3H6+ 2 NaCl + 3 B2H6
 Boron Nitrides
On a larger scale, the reaction of (NH2)2CO with B(OH)3 at high temperature in
an atmosphere of ammonia is used to produce borazine. Trichloroborazine,
B3N3Cl3H3 , has the structure

The chlorine atoms are bonded to boron atoms as expected on the basis of the
difference in electronegativity.