GROUP IIIA B, Al, Ga, In and Tl

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 BORON
Isotopes – Two are known: 10B (19.6%) 11B (80.4%).
• Crystalline B is extremely inert. Unaffected by boiling
HCl, HF.

• Slowly oxidized by Hot Conc, HNO3 when finely

powdered.

BORON – Principal ores are the Borates eg. Borax

[Na2B4O5(OH)4.8H2O]

EC = Is2 2s2 2p1

• No simple electron loss to form the cation, B3+

Therefore, Covalent bond formation is of major

importance.
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 TOXOLOGIST ADDITION
CONCEPT FROM BOOKS
• Factors for short bond in boron
• P-pie- p pie bond
• Stretching due to ionic covalent resonane
• Incomplete octate in boron

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NOTE: Boron is always trivalent and never
monovalent

Because – The total energy released in the formation

of three bonds in a BX3 compound exceeds the
energy of formation of one bond in a BX compound.

That is the energy needed to promote electrons prior to

hybridization is far less than that needed for
ionization.

Boron orbitals are hybridized to the sp2 type, in which

the three sp2 hybrid orbitals lie in one plane at 120o.
i.e. X-B-X = 120o.

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Diagonal Relationship, B and Si
The Chemistry of Boron resembles that of Si rather than that
of Al  Tl.
Examples: (More examples may be found in text books)
(1) B(OH)3 (Boric acid) is weakly acidic whereas Al(OH) 3 is
basic with some amphoteric properties.

(2) B & Si hydrides: - volatile, spontaneously flammable and

readily hydrolyzed. The only binary hydride of Al is a solid
polymeric material.

(3) B & Si halides (not BF3) are readily hydrolyzed. Al halides

are only partially hydrolyzed in water.

(4) B2O3 & SiO2 are acidic in nature and dissolve metallic
oxides on fusion to form borates and silicates.
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ACCEPTOR BEHAVIOUR
BX3 compounds
BX3: X = F, H, Cl, etc.
• In these compounds, Boron octet is incomplete.
• B = Is2 2s2 2p1

Therefore, these compounds behave as acceptors

(Lewis acids) in which boron achieves its maximum
co-ordination with approximately sp3 hybridization.
eg. (CH3)3NBCl3, (CH3)3PBH3 and (C2H5)2OBF3.

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BORON COMPOUNDS
1. Borides
These are compounds of B with elements less electronegative
than itself (usually metals) and metalloidal compounds like
those of B with eg. P, As, etc.
E.g. M4B, M3B, M3B4…..MB66

 They possess unusual physical and chemical properties.

e.g. The Thermal and Electrical conductivity of ZrB2 & TiB2 (mp
2980 oC) are approx.10 times greater than the metals and the
m.p. are >1000oC.
NOTE:
Borides do not conform to the ordinary concepts of valence either
in stoichiometry or in structure.
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2. Oxygen Compounds of Boron
B-O bond energy = 560–790 kJ/mol and therefore quite strong.
cf. B-F in BF3 = 640 kJ/mol.

a) B2O3 is the principal oxide.

 is acidic and reacts with water forming B(OH)3 [Boric acid].
 When fused, dissolves many metal oxides to give borate
glasses.

b) Borates.
These are compounds which occur naturally, with
stoichiometry like: KB5O8.4H2O, Na2B4O7.10H2O, CaB2O4.
 Their anion structures are cyclic or linear polymers.
e.g. K3B3O6 (See Structure) 8
c) Boric acid B(OH)3.
The hydrolysis of boron halides, hydrides etc. gives Boric
acid or its salts.
 A very weak exclusively monobasic acid which acts not as a
proton donor but as a Lewis acid, accepting OH-

ie. B(OH)3 + H2O  B(OH)4- + H+ pK = 9.00.

In concentrated solutions:
2B(OH)3 + B(OH)4-  B3O3(OH)4- + 3H2O.

• See reactions of B(OH)3 in your text books

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3. Trihalides of Boron, BX3 X = F, Cl, Br, I.
• All act as Lewis acids.
BF3 has greater resistance to hydrolysis than BCl 3 and BBr3.
BCl3 + 3H2O  B(OH)3 + 3HCl
• Lewis acid character: BF3  BCl3 < BBr3
• p- p interaction btwn vacant pz orbital on B and three filled pz
orbitals on the three X atoms.

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4. Boranes (Boron hydrides) and related compds.
B2H6, B4H10, B5H9 …. B10H14….B20H26

• Preparative methods are numerous and highly

varied.
• Most preps begin with diborane (B2H6) and involve
pyrolysis under a variety of conditions, and often in
the presence of hydrogen and other reagents.

E.g.(i) B10H14 obtained by pyrolysis of B2H6 (100oC)

(ii) B5H9 obtained by pyrolysis of B2H6 (250oC)
in the presence of H2.
Naming of Boranes:
In naming boranes, the number of borane atoms is
indicated by a latin prefix and the number of hydrogen
atoms is given by an arabic number in parentheses.
(i) pentaborane(9) = B5H9
(ii) pentaborane(11) = B5H11

NOTE
 Most boranes are extremely reactive due to their
electron deficient nature.

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 Structure and bonding in Boranes
In all the boranes there is a problem of Electron deficiency,

That is: There are NOT enough electrons to permit the

formation of conventional two centre-two electron
bonds (2c-2e) between all adjacent pairs of atoms.

THEREFORE:
1. Three types of Multi-centre bonding have been proposed:
• 3c-2e hydrogen bridge bond

• Open 3c-2e boron bridge bond

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• Closed 3c-2e boron bond

• Full Molecular Orbital theory may also be applied.

Diborane - B2H6
Preparation:
• By reacting LiH or NaH and a boron halide.
e.g. 6LiH + 2BF3 → 6LiF + B2H6
6NaH + BF3→ 6NaF + B2H6
• Properties:
Colourless gas (b.pt -90 oC)
Rapidly decomposed by water with formation of boric
acid and hydrogen. (i.e. vigorously hydrolysed).
B2H6 + 6H2O → 2B(OH)3 + 6H2
Ignite spontaneously in air
B2H6 + 3O2 → B2O3 + 3H2O
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 Bonding in Diborane, B2H6.
• The two boron atoms are each sp3 hybridized.

Terminal hydrogens:
 Two of the sp3 hybrid orbitals of each boron atom bonds with the
“terminal” hydrogen atoms which all lie in one plane. (Normal
covalent bonds i.e. 2c-2e bonds.

Bridge hydrogens:
• Thus, each boron atom is now left with two more sp 3 orbitals, but
with only one electron.
• Each of the two orbitals overlaps with the s-orbital of a “bridge”
hydrogen atom which also overlaps with the corresponding
orbital of the other boron atom forming a bonding orbital shaped
like a banana and extending over all THREE ATOMS.

• This orbital contains only two electrons, so it is called a “three

centre two electron bond” i.e. 3c-2e bond.
• The 3c–2e bond is only about half as strong as a conventional
2c–2e terminal B—H bond.
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 Derivatives of Boranes.
(i) The tetrahydridoborate ion: BH4- (Borohydride ion)
• The simplest of the borohydride anions.
• Prep. of borohydrides of some metals:
(a) 4NaH + B(OMe)3  NaBH4 + 3NaOCH3 (at ca. 250oC)
(b) 2LiH + B2H6  2LiBH4 (solvent = diethylether)

BH4- and the substituted derivatives, eg. [BH3CN]- and

[BH(OMe)3]- are widely used as reducing agents and sources of
H- .

(ii) Polyhedral borane anions and carbaboranes

a) Polyhedral borane anions: Bn Hn2- n may vary from 3-26
b) Carbaboranes may be considered to be derived from
Bn Hn2- by replacement of BH- by the isoelectronic and
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isostructural CH.
Example of 3c-2c bond

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Thus, two replacements result in Bn-2C2Hn = Carbaborane
Carbaboranes or their derivatives with n = 5 to n= 12 are
known.

Classes of Boranes and Carbaboranes

Five broad classes of boranes and carbaboranes are
recognized:
i. Closo- (closed) compounds, BnHn2- n = 6-12 and
Bn-2C2Hn; n = 5-12, eg. B9H92-
• Compounds in which the boron atom framework closes in
on itself to form a polyhedron with triangular faces.

ii. Nido- (nest-like) compounds eg. B10H14, B5H9

• Compounds in which the boron atom framework is open
or incomplete polyhedron. 19
iii. Arachno- (weblike), eg. B4H10.
• Molecules are obtained by removing, from the nido-
cluster, the highest connected boron atom of the open
face.

iv. Hypho- (netlike)

• Molecules are even more opened out than arachno or
nido molecules.

v. Conjuncto-
These have structures formed by linking two or more of
the four types of clusters together.
e.g. B15H23, B20H26

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 Structures of some carbaboranes
More structures may be found in your text books

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5. Compounds of boron with other elements
Boron also forms compounds with bonds to N, P, As, S, and C.

6. Borazine
The reaction between diborane and ammonia gives borazine,
B3N3H6 (inorganic benzene) which is analogous to benzene.
3B2H6(g) + 6NH3(g)  2B3N3H6(l) + 12H2(g)

• Has physical properties (boiling points, densities, surface tensions)

resembling Benzene.

• It is more reactive chemically and readily undergoes addition reactions

which do not occur with benzene:
B3N3H6 + 3HX  (-H2N-BHX-)3 X = Cl,OH,OR etc.

eg. B3N3H6(l) + 3HCl(g)  B3N3H9Cl3

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Inorganic benzene(borazene)

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 Al, Ga, In, Tl

EC IE (1st) Radii (A)

kJ/mol
M3+ M+

Al [Ne]3s23p1 576.4 0.50 -

Ga [Ar]3d104s24p1 578.3 0.62 1.13

In [Kr]4d105s25p1 558.1 0.81 1.32

Tl [Xe]4f145d10 6s26p1 589 0.95 1.40

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Occurrence
Al – obtained in accessible deposits as:
Bauxite (Al2O3.nH2O) and Cryolite (Na3AlF6 - sodium
hexafluoroaluminate).

Ga, In & Tl Found only in trace amounts.

Therefore, obtained by electrolysis of aqueous solutions of their
salts.

• Cationic complexes such as [Ga(H2O)6]3+ can be formed as well

as covalent compounds.

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Reactivity increases on descending the group.
• B reacts with other elements only at high
temperatures
• Al is less reactive due to protective oxide coating/film
(this oxide coating can be removed by
amalgamation with mercury)
• Ga, In & Tl generally are more reactive than B & Al

• Oxidation states
common oxidation state = +3
B, Al & Ga; +3 is more stable than +1 state
For In & Tl; +1 State is common
For Tl +1 state is the MOST STABLE

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 INERT PAIR EFFECT

THE APPEARANCE OF A VALENCE WHICH IS TWO

LESS THAN THE GROUP’S OXIDATION STATE.

• WHY?

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Inert pair effect:

Defn: The resistance of a pair of s electrons

to be lost or to participate in covalent bond
formation.

I.e. the s-electrons tend to be inert.

This effect is experienced by elements which

are lower in the group, especially thallium.

 Thallium readily forms Tl+ rather than Tl3+

because of the inertness of the s-
electrons.
The valence shell i.e. [Xe]4f145d10 6s26p1.

Sn, Pb and Bi also exhibit Inert pair effect.

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• The inert pair effect is the reluctance of s-electrons to
take part in bond formation. A chemical consequence
is the occurrence of oxidation states which are two
units less than the group oxidation.
• Let us understand this in detail.
• The electronic configuration of Group 13 elements is
ns2np1. Hence, they would be expected to be trivalent.
However for the heavy elements lower oxidation
states are more stable. This is explained by the s
electrons remaining paired and not

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• participating in bond formation. This
inertness of s-subshell electrons towards the
bond formation is called inert pair effect.
• This happens because the s orbitals are held
closer to the nucleus, therefore the electrons
present in s orbitals are held strongly by
nucleus because of large electrostatic forces.
Hence the energy required to unpair the s-
electrons is high because of which they
remain paired
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Reason: This happens due to the decreasing strengths of
bonds as we move down the group.

eg. MCl3:

M-Cl bond energy 2nd + 3rd IE

Ga = 242 kJ/mol Ga = 4916 kJ/mol
In = 206 kJ/mol In = 4501 kJ/mol
Tl = 153 kJ/mol Tl = 4820 kJ/mol

Hence there is an increasing drive for the reaction: MX 3 = MX + X2.

Known compd: eg. Tl2O.

NOTE- Compounds like Tl3+(Cl-)3 are not purely ionic and have
substantial covalent character 31
 BINARY COMPOUNDS
The trivalent state
1) Oxides
(a) The elements Al to Tl form oxides of the formula M2O3.
• B2O3-acidic, Al2O3 and Ga2O3-amphoteric,In2O3, Tl2O3-basic
(b) Mixed Oxides
Al, Ga and Tl also form MIXED OXIDES containing traces
of other metals.
e.g. Al2O3 containing traces of Cr3+, Fe2+, Fe3+ can be
manufactured.
c) Other mixed oxides containing macroscopic proportions
of other elements can also be made.
e.g. The minerals: (i) Spinel, MgAl2O4 and (ii) Crysoberyl,
BeAl2O4. 32
2) Halides.
MX3, M = Al, Ga, In. X = F, Cl, Br, I.
• Except Tl which is thallium(I) and not thallium(III) iodide.

• All of the trifluorides are non-volatile solids.

• The monomers MX3 X = Cl, Br are formed at high temps.

• AlCl3 is dimeric in the vapour phase.

• MI3; M = Al, Ga, In are dimeric.

• The halides dissolve readily in many non-polar solvents

(eg. benzene) in which they are dimeric. The dimers may
be split by reaction with donor molecules. 33
 DIMERS - M2X6 [M = Al, Ga, In & X = Cl,Br,I]

The formation of such dimers is attributable to the

tendency of the metal atoms to complete their octet.

X X X
x x x
x
Mx Mx

X X X

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3) The aqua ions:
The elements form [M(H2O)6]3+
 Sulphates, nitrates & perchlorates are known.
 The cations [M(H2O)6]3+ are acidic in aqueous solution.
[M(H2O)6]3+ = [M(H2O)5(OH)]2+ + H+

4) Alums.
General formula: MIMIII(SO4)2.12H2O
MI = Any common univalent monoatomic cation except
Li+ which is too small to be accommodated without loss of
stability of the structure.
MIII = Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Rh or Ir.
• E.g.: Potash alum – K+Al3+(SO42-)2.12H2O
Ammonium alum – NH4+Al3+(SO42-)2.12H2O
Ammonium iron(III) alum –NH4+Fe3+(SO42-)2.12H2O
Chrome alum –K+Cr3+(SO42-)2.12H2O 35
5. Hydroxides
 M(OH)3, M = Al or Ga are amphoteric.
 M(OH)3, M = In or Tl are purely basic.

6. Hydrides
 AlH3 is a colourless involatile solid extensively
polymerized via Al-H-Al bonds.

 Thermally unstable above 150-200o

 Reacts violently with water.

 Gallane, GaH3, is stable at about -50o and decomposes to

its elements at room temp.

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6) Complex hydrides.
The most important for Al & Ga are the
tetrahedral hydride ions:
AlH4-and GaH4- which are similar to BH4-.
The thermal and chemical stability are in the
order
BH4- > AlH4- >> GaH4-

Eg.
(i) LiGaH4 decomposes slowly at 25oC to LiH,
Ga and H2.
(ii) Although BH4- is slowly hydrolyzed in water,
the Al & Ga analogues are rapidly and often
explosively hydrolyzed by water.
MH4- + 4H2O  4H2 + M(OH)3 + OH-
37