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Group iii a (13)

he members present in gr III A are B, Al, Ga, In and Tl , having electronic

configuration , oxidation states and co-ordination no.s as tabulated bellow.

ELEMENTS

ELECTRONIC
OXIDATION COORDINATION
CONFIGURATION STATE
NO

ns2np1
Boron (B)
(He)2s22p1
Aluminium(Al) (Ne)3s23p1
Gallium (Ga)

(Ar)3d104s24p1

Indium (In)

(Kr)4d105s25p1
(Xe)4f145d106s26p1

Thallium (Tl)

III
(I) , III
I , III
I , III
I , III

3,4
3,4,6
3,(4), 6
3,(4), 6
3 , 6

The oxidation states or co-ordination no.s those are unstable or in doubt are given in
parentheses.

Electronic configuration and ionisation potential:For B and Al, it is the preceding noble gas configuration. For Ga and In it is
noble gas plus d10 , and for Tl noble gas plus 4f145d10 .This variation has a
substantial influence on the trends in chemical properties in the group and is also
reflected in the ionisation energies of the elements. Thus the expected decrease in I.E.
from B to Al is not followed by a further decrease to Ga because of the d-block
contraction in atomic size and higher effective nuclear charge for Ga which stems
from the fact that the ten added d electrons do not completely shield the extra +ve
charge on the nucleus. Similarly decrease between Ga and In is reversed for Tl
as a result of further influence of the f-block or lanthanide contraction.
8000

Ionisation energy
(kJ mol-1)

7000
6000

Variation of I.E. through

the group

5000
4000

3rd ionisation energy

3000

2nd ionisation energy

2000

1st ionisation energy

1000
0
B

Al

Ga

In

Tl

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Oxidation potential and electronegativity:The standard electrode potentials of the gr 13 elements reflect the decreasing stability
of +III oxidation state in aq. solution down the group and tendency to form
compounds in the +I oxidation state (a manifestation of inert pair effect).
There is a steady increase in electronegativity from Al to Tl.
Standard oxidation potential

2.5

1.5

1
0.5

1.5
EM3+/M

Pauling's electronegativity

ELECTRONEGATIVITY

1
0.5

0
-0.5

Al

Ga

In

Tl

-1

0
B

Al

Ga

In

Tl

-1.5
-2

Structure of elements:Boron is a covalently bonded , refractory , non-metallic insulator of great hardness

and differs in physical properties from Al , Ga , In , Tl which are all low melting ,
rather soft metals with high electrical conductivity.
The crystal structure of Al is fcc typical of many metals , each Al is surrounded by
12 nearest neighbours at 286 pm. Tl has a typical metallic structure (hcp) with 12
nearest neighbours at 340 pm. In has an unusual structure which is slightly distorted
from a regular close patched arrangement of a face centred tetragonal structure.

Lower halides of Boron:The formation of BX (X=F,Cl,Br,I) is difficult due to higher stability of BX3. BF3 (g)
when passed over heated crystalline boron at 1850oc under low pressure ( less than
1mm of Hg ) the reactive species {BF}(g) is obtained in high yield and can be
condensed out at -198oc
3BX (g) = BX3 + 2B

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Condensation of BF with BF3 (g) gives B2F4 , B3F5 (i.e.

).However the
o
latter is unstable and it disproportionate above -50 c to B2F4 and B8F12.
4

= 2B2F4 + B8F12

B8F12 is the dimer of B(BF2)3

and it is yellow in colour.

The molecule B8F12 has diborane like structure and undergoes symmetrical cleavage
in presence of variety of ligands like CO,PF3,PH3,AsH3,SMe2 to give L: B(BF2)3 ,
stable at room temperature in absence of air or moisture. B2Cl4 and B2Br4 at moderate
temperature give a series of closo halogeno boranes BnXn where n= 4 , 8-12.

All forms of compounds of stoichiometry B2X4 have been reported but only the
fluorides and specially the chlorides have been much studied.
In the crystalline state both B2F4 and B2Cl4 consists of BX2 groups joined by B-B
bonds and the molecules are planner (D2h) , whereas spectroscopic and electron
diffraction evidence suggests that in liquid and gaseous phase they are non-planner
with mutually perpendicular BX2 groups (D2d).
The following appears to be the most convenient preparative reactions.
BF3 (g) + 2B (crystal) = 3{BF}

-196oc (condensed)

2 (BO)X + 2x SF4 = x B2F4 + 2x SOF2

6 (BO)X + 4x BCl3 = 3x B2Cl4 + 2x B2O3
Low pressure

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2BCl3 + 2Hg

B2Cl4 + Hg2Cl2

Electrical arc

The reaction proceeds via the formation of {BCl} intermediate which then inserts
into a B-Cl bond of BCl3.
B2Cl4 and B2F4 readily add to acetylinic and olefinic linkage where B-B linkage is
cleaved. The rate of addition is greater for B2Cl4 with respect to B2F4 as the former
has greater lewis acidity character.
25oc

50oc

Anothgh the forof

Another route is through the formation of B2(NMe2)4 .

BCl3 + 2 B(NMe2)3

3BCl(NMe2)2

Dispersed with
molten Na

B2(NMe2)4
Acid
hydrolysis

B2Cl4

BCl3(g)

B2O2(s)

200oc

B2F4

Structure of B2Cl4

B2(OH)4

250oc
SF4

SbF5

vac

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Thermal stabilities of these compounds

bonding between the substituents.

reflects the extent of p -d

B2(NMe2)4 >B2(OMe)4 >B2(OH)4 >B2F4 >B2Cl4 >B2Br4

Boron trihalides:Boron forms many halides of which the monomeric trihalides BX3 are most stable
and most widely studied. The monohalides BX (X = F,Cl,Br,I) are
thermodynamically unstable due to disproportionation to BX3
The boron trihalides are volatile, highly reactive, monomeric and show no detectable
tendency towards dimerisation in contrast to other metal halides of gr-13 M2X6 [
M=Al ,Ga ,In and X=Cl ,Br ,I]
BF3, BCl3 are gaseous and BI3 is solid.
Preparation of BX3 :BF3, extremely used as a catalyst in different industrial fields, is prepared in large
scale by the fluorination of B2O3 or borates with fluorspar and conc.H2SO4.
6 CaF2 + Na2B4O7 + 8 H2SO4 = 6 CaSO4 + 4 BF3 + Na2SO4 + 7 H2O
Pure BF3 in laboratory is prepared by
PhN2BF4

PhF + N2 + BF3

Benzene diazonium fluoroborate

BCl3 and BBr3 are prepared by

B2O3 + 3C + 3Cl2
2BF3 + Al2Br6

500oc

2BCl3 + 3CO
2BBr3 + 2AlF3

Structure and bonding :The inter atomic distances B-X are substantially less than that expected for single
bonds and can be interpreted in terms of p
interaction.

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The extent of -bonding in BX3 is maximum in BF3 (due to orbital size similarity)
and decreases in the following order with the increase in orbital size difference
between B and X.

BF3 >BCl3 >BBr3 ~BI3

As a result the trend for lewis acidity follows almost the reverse order

BF3 <BCl3 <BBr3 ~BI3

Evidence of

-bonding in BF3 :-

The formation of BX4-, isoelectronic with BH4-, CH4 etc are

BF3 + HF = BF4- + H+
BF3 + BrF3 = BF4- + BrF2+
The lengthening of B-F bond from 130pm to 145pm on passing from
BF3 to BF4- proves the presence of - bonding in BF3

Central B is sp3 hybridised

Central B is sp2 hybridised

No

Extensive -bonding

-bonding

Factors affecting the stability of donor acceptor complex:For a given ligand, stability of the adduct L: BX3 usually increases in the sequence
BF3<BCl3<BBr3<BI3 probably because of the loss of -bonding on reorganisation
from planner (sp2) to tedrahedral (sp3) geometry is not fully compensated from the
expected electronegativity effect. However if the ligand has a H-atom directly bonded
to the doner atom , the resulting complex is susceptible to protonolysis of the B-X
bond e.g.

BX3

[ROH.BX3]

ROBX2 + HX

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In such cases the great strength of B-F bond ensures that the BF3 complex is more
stable than others. For example BF3 forms stable complexes with H2O ,MeOH
,Me2NH etc whereas BCl3 reacts rapidly to give B(OH)3 ,B(OMe)3 and B(NMe2)3.
With BBr3 and BI3 such protolytic reactions are something of explosive violence.
Even ethers may be cleaved by BCl3 to give RCl and ROBCl3 etc.
For a given BX3 ,the stability of the complex depends on

1. The chemical nature of the donor atom

2. The presence of polar substituents on the ligand
3. Steric effect
4. The stoichiometric ratio of ligand to acceptor
5. The state of aggregation

Halides and halide complexes:- (reactivities and oxidation states)

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