Main Group

Diborane and Borazine

IIT JAM Chemistry Short Notes Unit: Diborane and Borazine

MAIN GROUP CHEMISTRY

INTRODUCTION TO DIBORANE
Diborane (B2 H6 ) is the simplest stable member of the borane family. It is a quintessential example
of an electron-deficient molecule, where the total number of valence electrons is insufficient to form
conventional two-center two-electron (2c-2e) bonds between all adjacent atoms.
• Colorless, highly toxic, and spontaneously flammable gas.
• Lewis acid character due to vacant p-orbitals.
• Acts as a powerful reducing agent in organic synthesis.
• High heat of combustion (≈ −2035 kJ/mol).
Diborane → sp3 Hybridized Boron + 3c-2e Bonds → Banana Bonding

STRUCTURE AND BONDING

The bonding in Diborane is explained via Molecular Orbital Theory or the concept of Banana
Bonds. Each Boron atom undergoes sp3 hybridization, utilizing its three valence electrons and one
vacant orbital.

Geometric Features
• Planarity: The two Boron atoms and four terminal Hydrogen (Ht ) atoms lie in one plane.
• Bridging: Two Hydrogen atoms (Hb ) act as bridges, situated in a plane perpendicular to the B2 H4
plane.
• Bond Nature: There are 4 terminal 2c-2e bonds and 2 bridging 3c-2e bonds.

Figure 1: *
Structure of Diborane showing Ht and Hb atoms.

Comparative Bonding Table

Feature Terminal (B − Ht ) Bridging (B − Hb )
Bond Type 2-center 2-electron (2c-2e) 3-center 2-electron (3c-2e)
Bond Length 1.19 Å (Shorter) 1.33 Å (Longer)
Bond Angle ̸ Ht − B − Ht ≈ 120◦ ̸ B − Hb − B ≈ 83◦
Electron Count 2 Electrons per bond 2 Electrons per 3 nuclei

1
IIT JAM Chemistry Short Notes Unit: Diborane and Borazine

Figure 2: *
Structure of Diborane

METHODS OF PREPARATION
• Laboratory Method: By the reaction of I2 with N aBH4 in polyether.
2N aBH4 + I2 → B2 H6 + 2N aI + H2
• Industrial Method: By the reduction of BF3 with Sodium Hydride.
450K
2BF3 + 6N aH −−−→ B2 H6 + 6N aF
• Magnesium Boride: Reaction with acids.
M g3 B2 + 6HCl → 3M gCl2 + B2 H6

CHEMICAL REACTIONS
The reactivity of Diborane is dominated by the cleavage of the electron-deficient bridge.

Cleavage Reactions (Symmetrical vs Unsymmetrical)

1. Symmetrical Cleavage: Large, bulky Lewis bases (e.g., N M e3 , T HF , CO) split the molecule
into two BH3 · L fragments.
2. Unsymmetrical Cleavage: Small, strong Lewis bases (e.g., N H3 at low T, CH3 N H2 ) yield ionic
products.
Reagent Type of Cleavage Final Product
N (CH3 )3 Symmetrical 2H3 B · N (CH3 )3
CO Symmetrical 2H3 B · CO
N H3 (Low T) Unsymmetrical [BH2 (N H3 )2 ]+ [BH4 ]−

Formation of Inorganic Benzene (Borazine)

Heating the unsymmetrical cleavage product of N H3 at high temperatures (450 K) results in Borazine
(B3 N3 H6 ).
∆
3[BH2 (N H3 )2 ]+ [BH4 ]− −
→ 2B3 N3 H6 + 12H2

2
IIT JAM Chemistry Short Notes Unit: Diborane and Borazine

WADE’S RULES FOR BORANES

Wade’s rules allow prediction of the shape of borane clusters based on Skeletal Electron Pairs (SEP). For
a formula Bn Hnz :
• Closo: SEP = n + 1 (General formula: [Bn Hn ]2− )
• Nido: SEP = n + 2 (General formula: Bn Hn+4 )
• Arachno: SEP = n + 3 (General formula: Bn Hn+6 )
Note: Diborane (B2 H6 ) is classified as an **Arachno** borane.

INTRODUCTION TO BRIDGE BONDING

Bridge bonding occurs when an atom or a group of atoms connects two or more central atoms. This is
a hallmark of electron-deficient compounds where the number of valence electrons is insufficient to
form standard 2-center 2-electron (2c-2e) bonds between all adjacent atoms.
• Essential for stability in Group 13 elements (B, Al).
• Involves delocalization of electron density over multiple nuclei.
• Categorized primarily into 3c-2e and 3c-4e bonds.
Bridge Bond → Central Atom 1 + Bridging Ligand + Central Atom 2 → Multi-center Bonding

DIBORANE (B2 H6 )
Diborane is the most significant example for bridge bonding. Boron ([He]2s2 2p1 ) has 3 valence electrons.
B2 H6 has a total of 12 valence electrons, but 14 are required for a standard ethane-like structure.

Structural Characteristics
• Terminal Bonds: 4 B − H bonds (2c-2e).
• Bridge Bonds: 2 B − H − B bonds (3c-2e or ”Banana Bonds”).
• Hybridization: Each Boron is sp3 hybridized.
• Geometry: 4 terminal Hydrogens and 2 Borons are coplanar; bridging Hydrogens are perpendic-
ular to this plane.

ALUMINIUM CHLORIDE DIMER (Al2 Cl6 )

In the vapor phase, AlCl3 exists as a dimer. Unlike Boranes, Chlorine has lone pairs, changing the nature
of the bridge.
• Each Al atom accepts a lone pair from a Cl atom attached to the other Al.
• This forms a 3c-4e bond system.
• The bridge is formed by coordinate covalent bonds.

Figure 3: *
Structure of Al2 Cl6

3
IIT JAM Chemistry Short Notes Unit: Diborane and Borazine

BRIDGING IN ORGANOMETALLICS
Trimethylaluminium [Al(CH3 )3 ]2
The methyl group (CH3 ) can also act as a bridging ligand.
• Formed via 3c-2e bonds.
• The Al − C − Al bond angle is small ( 75◦ ) due to the constraints of the 3-center orbital overlap.

Figure 4: *
Structure of [Al (CH3 )3 ]2

Beryllium Hydride (BeH2 )n

• A polymeric solid with infinite chains.
• Each Be is surrounded by 4 Hydrogens in a tetrahedral arrangement (sp3 ).
• All Be − H − Be bonds are 3c-2e bonds.

Figure 5: *
Structure of (BeH2 )n

SUMMARY COMPARISON
Molecule Bond Type Hybridization Bond Type
B2 H6 3c-2e sp3 Banana Bond
Al2 Cl6 3c-4e sp3 Coordinate Bridge
BeCl2 (Vapor) 3c-4e sp2 Dimeric
[Al(CH3 )3 ]2 3c-2e sp3 Alkyl Bridge

4
IIT JAM Chemistry Short Notes Unit: Diborane and Borazine

HIGHER BORANES & WADE’S RULES

To determine the structure of larger clusters where bridge bonding is prevalent:
• Closo: [Bn Hn ]2− (Closed cage)
• Nido: Bn Hn+4 (Nest-like, one vertex missing)
• Arachno: Bn Hn+6 (Spider-web like, two vertices missing)

INTRODUCTION TO BORAZINE
Borazine, also known as Inorganic Benzene, is a cyclic inorganic compound isoelectronic and isostruc-
tural with benzene (C6 H6 ). It consists of alternating Boron and Nitrogen atoms in a six-membered ring.
Its study is vital to understand the differences between organic aromatic systems and inorganic polar
systems.
• Molecular Formula: B3 N3 H6
• Isoelectronic: Both Borazine and Benzene have 42 total electrons (30 valence electrons).
• Nature: Colorless liquid with an aromatic-like smell.
Borazine → Isostructural to Benzene + Polar Bonds → Higher Reactivity

METHODS OF PREPARATION
• Stock and Pohland Method: Reaction of Diborane and Ammonia in a 1:2 ratio.
200◦ C
3B2 H6 + 6N H3 −−−−→ 2B3 N3 H6 + 12H2

• From Boron Trichloride: A more modern route involving ammonium chloride.

∆
3N H4 Cl + 3BCl3 −
→ B3 N3 H3 Cl3 + 9HCl

(The resulting trichloroborazine is then reduced using N aBH4 to give Borazine.)

STRUCTURE AND BONDING

Electronic Characteristics
• Hybridization: All B and N atoms are sp2 hybridized.
• Back-Bonding: The filled pz orbital of Nitrogen overlaps with the vacant pz orbital of Boron
(pπ − pπ bonding).
• Polarity: Unlike the non-polar C − C bonds in benzene, the B − N bonds are highly polar due to
the electronegativity difference (χN > χB ).

5
IIT JAM Chemistry Short Notes Unit: Diborane and Borazine

Figure 6: *
Structure of Borazine

Comparison Table: Borazine vs. Benzene

Feature Borazine (B3 N3 H6 ) Benzene (C6 H6 )
Bond Type Polar (B δ+ − N δ− ) Non-polar (C − C)
Electrons 42 Total (30 Valence) 42 Total (30 Valence)
Bond Length 1.44 Å (Equal) 1.39 Å (Equal)
Reactivity High (Addition reactions) Low (Substitution reactions)
Aromaticity Partial / Lower Full / Higher

CHEMICAL REACITIVITY
Borazine is much more reactive than benzene. The polarity of the B − N bond allows for easy addition
of polar molecules.

1. Addition Reactions
Nucleophiles attack the electron-deficient Boron, while electrophiles attack the electron-rich Nitrogen.
• Addition of HCl: Forms B3 N3 H9 Cl3 . Chlorine attaches to B; Hydrogen attaches to N.

B3 N3 H6 + 3HCl −→ B3 N3 H9 Cl3

• Hydrolysis: Reacts with water to form Boric Acid and Ammonia.

B3 N3 H6 + 9H2 O → 3H3 BO3 + 3N H3 + 3H2

2. Stability
Borazine is thermally less stable than benzene and decomposes at higher temperatures, whereas benzene
remains stable up to very high temperatures.

Quick Revision Summary

• All B − N bond lengths in Borazine are identical due to delocalization.
• Nitrogen acts as a π-donor and Boron as a π-acceptor.
• Borazine undergoes **Addition Reactions** readily, whereas Benzene prefers **Electrophilic Sub-
stitution**.

PW Web/App - [Link] 6
Library - [Link]
 Main Group
Carbides and Silicates
IIT JAM Chemistry Short Notes Unit: Carbides and Silicates

MAIN GROUP CHEMISTRY

CARBIDES
Carbides are binary compounds of carbon with elements of lower or similar electronegativity. They are
primarily classified by their bonding nature and their behavior upon hydrolysis.

1. Ionic (Salt-like) Carbides

These are formed by highly electropositive metals (Groups 1, 2, and 13). They are further divided based
on the hydrocarbons they produce during hydrolysis:
• Methanides: Contain discrete C 4− units.
– Examples: Be2 C, Al4 C3 .
– Reaction: Al4 C3 + 12H2 O → 4Al(OH)3 + 3CH4 ↑
• Acetylides: Contain C22− units ([C ≡ C]2− ).
– Examples: CaC2 , M gC2 .
– Reaction: CaC2 + 2H2 O → Ca(OH)2 + C2 H2 ↑
• Allylides: Contain C34− units.
– Example: M g2 C3 .
– Reaction: M g2 C3 + 4H2 O → 2M g(OH)2 + CH3 C ≡ CH ↑ (Propyne)

2. Covalent and Interstitial Carbides

• Covalent: SiC (Carborundum) and B4 C. Extremely hard, diamond-like structures.
• Interstitial: Formed by Transition Metals. Carbon fits into the holes of the metal lattice. They
retain metallic conductivity.

SILICATES
The structural unit of all silicates is the tetrahedral [SiO4 ]4− unit. Silicon is sp3 hybridized. Silicates
are classified based on the number of oxygen atoms shared per tetrahedron.

Classification Table
Silicate Type Shared O atoms General Formula Example
Orthosilicate 0 SiO44− Zircon (ZrSiO4 )
Pyrosilicate 1 Si2 O76− Thortveitite
Cyclic/Chain 2 (SiO3 )2n−
n Beryl / Pyroxenes
Sheet 3 (Si2 O5 )2n−
n Talc / Mica
3D Framework 4 (SiO2 )n Quartz / Zeolites

Structural Notes
• Orthosilicates: Discrete units; no oxygen sharing.
• Pyrosilicates: Two units share one oxygen atom (vertex).
• Zeolites: 3D Aluminosilicates where Si4+ is replaced by Al3+ . Used as ”Molecular Sieves” and in
”Shape Selective Catalysis” (ZSM − 5).

1
IIT JAM Chemistry Short Notes Unit: Carbides and Silicates

SILICONES (Organosilicon Polymers)

Silicones are synthetic polymers containing (R2 SiO) units held by Si − O − Si linkages.

Synthesis Steps
Cu/300◦ C
1. 2RCl + Si −−−−−−→ R2 SiCl2 (Dialkyl dichloro silane)
2. R2 SiCl2 + 2H2 O → R2 Si(OH)2 + 2HCl
3. Polymerization: Condensation of Silanols leads to linear silicones.

Structural Control
• Chain Termination: Add R3 SiCl to stop the chain.
• Cross-linking: Add RSiCl3 to produce a 3D network.

PW Web/App - [Link]
Library - [Link]

2
 Main Group
Phosphazenes and Sulphazenes
IIT JAM Chemistry Short Notes Unit: Phosphazenes and Sulphazenes

MAIN GROUP CHEMISTRY

PHOSPHAZENES (Phosphonitrilic Compounds)

Phosphazenes are a class of organometallic/inorganic compounds containing alternating Phosphorus and
Nitrogen atoms with two substituents on Phosphorus. The general formula is (N P X2 )n .

1. Synthesis of Cyclic Trimers

The most important trimer, Hexachlorocyclotriphosphazene, is prepared by the reaction of P Cl5
and N H4 Cl in a high-boiling solvent like chlorobenzene.
120−150◦ C
3P Cl5 + 3N H4 Cl −−−−−−−→ N3 P3 Cl6 + 12HCl

2. Structure and Bonding

• Hybridization: Both P and N are sp2 hybridized.
• Bonding: The π-bonding is dπ − pπ in nature. The lone pair on Nitrogen (p-orbital) is donated
into the vacant d-orbitals of Phosphorus.
• Aromaticity: Unlike Benzene, the π-system is not fully delocalized in a continuous cloud. It is
often described as a ”node-at-P” system.
• Geometry: Planar or near-planar 6-membered ring with equal P − N bond lengths.

Figure 1: Structure of N3 P3 Cl6

3. Nucleophilic Substitution
Chlorine atoms in N3 P3 Cl6 are susceptible to nucleophilic attack.
• Geminal Substitution: Both Cl on the same P atom are replaced first.
• Non-Geminal Substitution: Cl atoms on different P atoms are replaced sequentially.

SULPHUR-NITROGEN COMPOUNDS (Sulphazenes)

The most significant compound in this category is Tetrasulphur Tetranitride (S4 N4 ).

1
IIT JAM Chemistry Short Notes Unit: Phosphazenes and Sulphazenes

1. Synthesis of S4 N4
Prepared by reacting S2 Cl2 with Ammonia.
6S2 Cl2 + 16N H3 → S4 N4 + S8 + 12N H4 Cl

2. Structure of S4 N4
• Geometry: Adopts a cradle-like or ”caged” structure.
• S-S Interactions: Features cross-ring S · · · S transannular interactions ( 2.58 Å), which are shorter
than Van der Waals distances.
• Properties: Thermochromic solid; changes color from pale yellow to orange upon heating.

Figure 2: Structure of S4 N4

3. Polythiazyl (SN )n
Formed by the polymerization of S2 N2 .
• Significance: It is a one-dimensional conductor becomes a superconductor at 0.26 K. It is the first
example of a non-metallic inorganic superconductor.

Figure 3: Structure of Polythiazyl

COMPARISON TABLE
Feature Phosphazene (N3 P3 Cl6 ) Sulphazene (S4 N4 )
Hybridization sp2 (P and N) Non-planar / Complex
Bonding Type dπ − pπ delocalization Transannular S − S bonds
Stability Thermally stable up to 250◦ C Shock-sensitive / Explosive
Conductivity Insulator (Polymer is elastomer) Metallic conductor / Superconductor

PW Web/App - [Link]
Library - [Link]