Gr 13

Borides
• Compounds of boron and less electronegative elements (metals and
metalloids)
• Composition and structure of metal borides are exceedingly varied
(M4B, M3B to MB66, MB50) from metal rich to very boron-rich
compounds.
• Extremely hard, high melting point, inert to air and mineral acids, high
thermal conductivity
• Some metal borides (TiB2) have electrical conductivities far exceeding
those of the metal itself
Non-metal borides: Boron Carbides
• Varying composition B13C2 to B24C: narrow band semiconductors
• Can be prepared by reduction of B2O3 with C in an electric furnace
• Industrial use: abrasive (nearly as hard as diamond)
in bullet-proof vests
in armor for aircraft
as a neutron absorber in nuclear reactors
Diborane B2H6
• Contains 4 terminal B-H
• Two 3-centre B-H-B bridge bonds (single electron pair to bind 3 atoms
together)
Boron-Nitrogen Compounds
• BN unit is isoelectronic with CC and the electronegativity and atomic
radius of carbon are almost exactly intermediate between the values
of N and B.
• There are many azaborane analogues of hydrocarbon in which B and
N replace a pair of C atoms
• Borazine has benzene-like structure, stabilized by π-delocalization
• Borazine is much more reactive than benzene owing to partial charges
on B and N
Boron Nitride (BN)
• BN, like carbon, has multiple structural forms. BN’s most stable
structure, BN is isoelectronic with graphite and has the same
hexagonal structure with similar softness and lubricant properties. BN
can also be produced in graphene-like sheets in which the hexagonal
rings are aligned in eclipsed fashion rather than staggered in graphite.
• In contrast, cubic BN (cBN) is isoelectronic with
diamond. It is not quite as hard, but it is
more thermally and chemically stable.
Group 13 in hydrogen storage
• Efficient fuel cells demand efficient source of hydrogen
• Chemical compounds that generate H2 on heating or on reaction with
water can also be used
• Boron and aluminium hydrides are such compounds
• LiBH4 (18%), NaBH4 (11%), LiAlH4 (11%) contains high mass percentage
hydrogen content
• Mg(BH4)2.2NH3 contains 16% hydrogen by mass and can release H2
when its solution is passed over a ruthenium catalyst at or above
150°C
Superconductors
• MgB2 loses its electrical resistance when cooled.
• In bulk materials the transition temperature is 38 K
• The boron atoms form honeycombed layers, and the magnesium
atoms are located above the centre of the hexagons in-between the
boron planes
• Superconductivity arises when a superconducting material is cooled to
a fairly low critical temperature. Suddenly, an electric current can then
flow with no resistance.
Boron Neutron Capture Theory
• Radiotherapy for brain tumours involve the irradiation of boron
compounds with low-energy neutrons.
• BNCT is emerging as a hopeful tool in treating cancer, by selectively
concentrating Boron compounds in tumour cells and then subjecting
the tumour cells to epithermal neutron beam radiation which
selectively destroys the tumour cells.
Boron Trihalides
• Aluminum trihalides form dimers Al2X6 to complete the valence octet
• In contrast, BX3 s are monomeric
• Here, backdonation of non-bonding electrons from halogens into the
pz orbital of boron lends some double bond character to B-X bond and
stabilizes the monomer.
• All the BX3 s are Lewis acids, but the acid strength decreases going
from BBr3 to BF3.
Boron Trihalides
• Rapid halogen exchange takes place on mixing two different trihalides
to form equilibrium mixtures of mixed-halogen species.
BCl3 + BBr3 → BCl2Br + BClBr2
• BF3 forms adducts with a variety of electron pair donors including
water, alcohols, ethers and amines.
BF3 + H2O → BF3.H2O or BF3.2H2O
BF3 + NH3, NR3 → BF3.NH3, BF3.NR3
BF3 + ether → BF3.OR2
Boron Trihalides
• BCl3, BBr3, BI3, in contrast to BF3, are rapidly hydrolyzed by water to
generate B(OH)3 and HX
• In dilute solutions, BF3 forms BF4- anions
• 4BF3 + 6H2O → 3H3O+ +3BF4- + B(OH)3
• BX3 + H2O → B(OH)3 + 3HX , in case of X = Cl, Br, I
Subhalides
• Boron-halogen compounds containing B-B bonds, in which halogen:
boron ratio is <3.
• B2X4 are known for all halogens, consist of two BX2 groups
joined by a B-B single bond.
• In case of B2Cl4 and B2Br4, the structure is staggered in the
gas phase but planar in solid state indicating of facile rotation around

single B-B bond