B

Al Group 13 Elements
Ga
Boron Group Elements
In

Tl

171
 General Properties
• Electronic configuration: ns2p1
• Al, Ga, In and Tl all form a range of compounds in +III oxidation
state, and compounds in +I oxidation state become more stable
down the group.
– Although the ionization energy decreases down the group with
increasing atomic radius, the heavier elements also show greater
stability of M+ (ns2p0). One possible explanation is that the ns2 electrons
are harder to remove due to relativistic contraction  thermodynamic 6s
Inert pair effect for Tl.
• The oxides of Al and Ga are amphoteric; In and Tl oxides are more
basic.
• The MX3 compounds are Lewis acids with decreasing acid strength
in the order of Al > Ga > In.
• Elements are strongly oxophilic and fluorophilic and mainly exist in
nature as oxide. The heavier In and Tl exist as sulfides.
172
Selected physical Properties

173
 Boron (B)
• Boron is the only non-metal in group 13.
• B was discovered in 1808 by Louis-Joseph Gay-
Lussac in France, and independently by Humphrey
Davy in England as the product of reduction of boric
acid with K or electrolysis. Both discovered not pure
boron, but a boron compound of ~60% boron.
Glassy Boron
• The name “boron” is derived from “borax”, which has
been known in the ancient times and “carbon”, to
indicate the “similarity” between the 2 elements.
• It occurs naturally only in its oxygen compounds, e.g.
H3BO3 (boric acid), Na2B4O7•4H2O (kernite) and
Na2[B4O5(OH)4]•8H2O (borax).
Borax
• Properties: semiconducting, on the border between Na2[B4O5(OH)4]•8H2O
metal (Be) and nonmetal (C).

174
 Preparation of Boron
• Pure crystalline boron (>99.9%) can be prepared from
reduction of boron chloride or bromide with hydrogen:
2 BCl3(g) + 3 H2(g)  B(s) + 6 HCl(g)
(E. Weintraub 1909)
• Amorphous boron (98%) can be prepared by reduction
of B2O3 with Mg:
B2O3 + 3 Mg  2 B + 3 MgO
• Artem Oganov: "Boron is a truly schizophrenic element.
It's an element of complete frustration. It doesn't know
what it wants to do. The outcome is something horribly
complicated."  E.g. 16 crystalline allotropes of boron!
175
 Boron Chemistry
• The chemistry of B is quite different from that of the
heavier Group 13 elements. It differs from Al in the
following ways:
– Its oxide and hydroxide are acidic, whereas those of Al are
amphoteric.
– Boron is a semiconductor, whereas the other group 13 elements
are metals .
– No simple salt of B is known, whereas those of Al3+ are
numerous.
– Multiple p-p bonding in B-N, B-O and B-F compounds is much
more significant than that for the corresponding Al compounds.

176
 Boron-oxygen compounds
• Boron has high affinity for oxygen
• Boron-oxygen compounds
 +III oxidation state Boric acid

• Examples
– diboron trioxide: B2O3
– Boric acid: H3BO3 = B(OH)3

O B

Trigonal planar (sp2), Lewis acidic intermolecular H-bond

177
 Acidities of Boric Acid
B(OH)3 is a weak Lewis acid and a very weak Brønsted acid.

< 130 °C HO O OH
pKa 9.24 B(OH)3 -HBO2 B B
metaboric acid O O
B
Lewis acidity H2O
OH

500 °C
OH2 OH
H2O
B OH B OH
HO - H3O HO B2O3
OH OH

Brønsted acidity
178
Some Applications of Boric Acid
Cockroach “motels” contain solid
bait, which has boric acid as the
active ingredient.

Not permitted!
Boric acid was added to fish ball and
noodles as a preservative. A desirable
side effect – fish ball becomes more
elastic. A recent Malaysian study showed
that boric acid content in yellow noodle,
fish ball, wanton noodle, kway teow are
3 mg/g, 1.5 mg/g, 1 mg/g and 0.8 mg/g,
respectively.
179
 Boron Halides (BX3)
• Lewis acids
• Synthesis: from B2O3 or directly from boron
B2O3 + 6 HF  2 BF3 + 3 H2O
B + 1.5 Cl2  BCl3
D
X
X
B X + D B
X
Lewis acid Donor/Ligand
X
X
-donation

In the adducts D-BX3, the B atom would withdraw electron density from
the D. If D contains dissociable H such H2O, the complexation with
BX3 increases the acidity of the D.  e.g. BF3(OH2) is a strong acid.
180
Example: Boron Trichloride BCl3
• Preparation in laboratory:
BF3 + AlCl3  BCl3 + AlF3
• Properties: BCl3 is a colorless gas, which reacts
vigorously with excess water (hydrolysis).
BCl3 + 3 H2O  B(OH)3 + 3 HCl
• Corresponding reactions with NH3, ROH, and
RSH produce B(NH2)3, B(OR)3 and B(SR)3.

181
 Boron(II) halides B2X4 (X = F, Cl, Br)

Preparation: Reduction of BX3 with Hg or Cu

2 BCl3 + Hg  B2Cl4 + HgCl2

Cl

sp2 hybridized Cl
trigonal planar B B Staggered in gas phase

Cl Cl

The tendency of B to form B-B bonds is less pronounced than that of carbon,
its periodic table neighbor on the right, to form C-C bonds. However, it is much
greater than that of the nearest element in the group, Al, to form Al-Al bonds.

182
 Boron Hydrides
• BH3 cannot be isolated (cf. halides BX3). Why?
• 2 x “BH3” dimerizes to form B2H6 (diborane), a flammable, colorless
gas; b.p. = -92 °C; m.p = -165 °C
• Synthesis via metathesis of BCl3 or BF3 with hydride transfer
compounds:
4 BCl3 + 3 LiAlH4  2 B2H6 + 3 LiAlCl4
4 BF3 + 3 NaBH4  2 B2H6 + 3 NaBF4

What is the structure of diborane?

Two proposed structures
H H H H
H H
B B B B
H H
H H H H
"Ethane"-like Bridging Hydride
Linus Pauling giving a lecture on unresolved mystery of structural chemistry in 1947.
183
 Bonding Description
a) Total number of “Bonds” in ethane-like case = 7
Number of electrons required according VB theory = 7 x 2 = 14
b) Total number of “Bonds” in bridged case = 8
Number of electrons required according VB theory = 8 x 2 = 16
 Number of valence electrons in diborane = 2 x 3 + 6 = 12
Valence bond theory fails to provide a suitable bonding picture for B2H6,
since it requires two electrons in each bond.

J. Chem. Soc., 1943, 250.

In 1943, undergraduate Longuet-Higgins at Oxford University, proposed the

correct bonding picture for diborane, which invokes 3-center-2-electron bonds. 184
Three-Center-Two-Electron Bond 1

Bridging H
2c-2e bond

Terminal H 3c-2e bond

185
 Three-Center-Two-Electron Bond 2
A Simplified MO Description of three-center-two-electron bond

antibonding orbital
2 nodes

Energy
Nonbonding orbital

1 node

Bonding orbital
No node B H B
2 electrons reside in the
3 combinations of 3 atomic orbitals
bonding orbital and delocalize
give rise to 3 MOs: 1 bonding, 1
over the B–H–B linkage.
nonbonding and 1 antibonding. 186
 Lewis Acidity of Diborane

H H H CH3
H H
B B + 2 NMe3 2 B N
H CH3
H H H CH3
Borane-trimethylamine
complex
H H H
H H Li
B B + 2 LiH 2 B H
H
H H H Lithium-tetrahydridoborate(III)
aka Lithium borohydride
+2H
H2
187
 Some Applications
H H H
H H H
B H C H N H

H H H
Hydridic Neutral Protic

Tetrahydridoborate is a hydride transfer reagent and thus a reducing reagent.

188
 Some Applications
“Hydride Sponge”

H
BMe2 BMe2 Me2B BMe2

H-

“Proton Sponge”

H
NMe2 NMe2 Me2N NMe2

H+

189
 Aluminum/Aluminium (Al)
• Al is the most abundant metal in the earth’s crust
• Named after the mineral Alum (KAl(SO4)2•12H2O)
• Discovered by Danish chemist Hans Christian Ørsted in 1825.
AlCl3 + 3 K  Al + 3 KCl
• Because of its strong affinity for oxygen, Al naturally occurs only in
oxidized form such as Al2O3 (corundum) or Al(OH)3 (Gibbsite).
• Corundum with transition metal impurities are precious gem stones!
• Common oxidation state is +III; some AlI compounds are known.

Sapphire
Ruby Fe-containing Al2O3 Gibbsite
Hans Christian Ørsted Cr-containing Al2O3 190
 Preparation of Aluminium: Bayer Process
• 1. Step: Bayer Process (named after its inventor Karl Bayer)
• Red Bauxite (mix of Al2O3, Al(OH)3, AlO(OH), Fe2O3, SiO2 and other
oxides) is treated with NaOH, which form soluble Na[Al(OH)4], while
other hydroxides are insoluble.
NaOH + Al(OH)3  Na[Al(OH)4] soluble
NaOH + Fe(OH)3  Na[Fe(OH)4] insoluble

Dilution of the basic filtrate

leads to precipitation of Al(OH)3.

2 Al(OH)3  Al2O3 + 3 H2O Dehydration by heating!

191
 Preparation of Aluminum: Hall-Héroult-
Process
• 2. Step: Hall-Héroult-Process
Electrolysis of Al2O3 in molten Na3[AlF6] (cryolite) ( 7-12% Al2O3)
Al2O3  2 Al3+ + 3 O2- melting
2 Al3+ + 6 e-  2 Al cathode-process
3 O2-  1.5 O2 + 6 e- anode-process
Al2O3  2 Al + 1.5 O2 simplified overall process

192
 Applications and Red Mud Spill

Ajka, Hungary, 4th October 2010

There is currently no proper use for red sludge!

Use less and recycle Aluminum.

http://en.wikipedia.org/wiki/Ajka_alumina_plant_accident 193
 Use and Reactivity of Al2O3
• Al2O3 is often used as catalyst (e.g. Claus process) or
catalyst support for a variety of reactions.
• Al2O3 is commonly used as a stationary phase in column
chromatography for separation (alumina)
• Al2O3 is an amphoteric oxide and reacts with hot dilute
HCl to give AlCl3:
Al2O3 + 6 HCl  2 AlCl3 + 3 H2O
• With hot, concentrated NaOH solution, Al2O3 reacts to
give a colorless solution of sodium
tetrahydroxidoaluminate(III):
Al2O3 + 2 NaOH + 3 H2O  2 Na[Al(OH)4]

194
 Aluminum hydroxide and Aqua complexes

• Al(OH)3 is amphoteric and dissolves in both acids and

bases:
Al(OH)3 + OH–  [Al(OH)4]– basic solution
Al(OH)3 + 3 H+  Al3+ + 3 H2O acidic solution
• Dissolving AlCl3 in water gives [Al(OH2)6]Cl3 which is a
weak aqua acid (pKa = 4.97) of comparable acidity to
acetic acid
3+ 2+
OH2 OH
H2O OH2 H 2O OH2
Al Al + H+
H2 O OH2 H2O OH2
OH2 OH2
195
 Aluminum Hydrides
• Preparation:
3 LiAlH4 + AlCl3  3 LiCl + 4 AlH3 (alane)
LiAlH4 + HCl  LiCl + AlH3 + H2

• Unlike B2H6, AlH3 exists as a polymer (AlH3)n, in which each Al is

bonded to 6 H atoms; each H atom bridges two Al atoms.
• Analogous to BH4-, AlH4- is tetrahedral and a reducing and hydride
transfer agent. LiAlH4 (lithium aluminum hydride) is commonly used
in organic synthesis because of its solubility in ether.

H
H+
Al
-AlH3
H - H2
H Al
H H
196
 Aluminum Halides
• Preparation:
2 Al + 6 HX  AlX3 + 3 H2 (X = F, Cl, Br, I)
• Structures:
– AlF3 and AlCl3 are conducting salts in the solid state
– Liquid and gaseous AlCl3 exists as a dimer Al2Cl6
– Al2Br6 and Al2I6 have analogous structures
– Similar structures: Ga2X6 (X = Cl, Br, I), In2I6, Tl2Br6
• Reactivity:
– All AlX3 are Lewis acids that forms adducts with donors.
– Lewis acidity of AlCl3 is used to promote Friedel-Crafts acylation

Cl O O R
R Cl
Al Al
Cl AlCl3 catalyst
Cl Cl
OEt2
Friedel-Crafts acylation
Diethyl ether adduct 197