Chemical Bonding

• Introduction to intermolecular forces:

• Vander Waal forces, three types of forces, explanation, London dispersion force eg. Cl2
• Dipole-Dipole forces eg. HCl
• Hydrogen bonding eg. Water, o-nitrophenol and p-nitrophenol

• Types of bonding:
• Ionic bond (eg. KCl): Bond formation, characteristics
• Covalent Bond (eg.H2, HCl): Bond formation, characteristics
• Coordinate bond (eg. SO2/NH4+): Bond formation, characteristics
• Magnetism in coordination compounds
A chemical bond represents a strong force of attraction between two atoms.

Lewis’s octet rule: Atoms of all elements have a tendency to acquire an electronic configuration similar
to that of inert gases because it represents the most stable electronic configuration.

The requirement of electron pairing are mainly accomplished by the following modes:
• By complete transfer of one or more electrons from one atom to another this results in the
formation of ions and hence is called ionic bonding.
• By sharing of electrons between the two combining atoms, which results in the formation of a
covalent bond.
• A special type of covalent linkage in which both the shared electrons are contributed by one atom
only to give a coordinate covalent bond.
 IONIC BOND:
• Formed by the transfer of electrons from one atom to another.
• The atom which losses electrons acquires positive charge and contracts
• The atoms which gains electrons acquires negative charge and increases in size.
• The cation and anion thus produced are held together by electrostatic lines of force and hence the
linkage is called electrovalent bond and the compound so produced is called an electrovalent
compound. Since ions are held together we often call these ionic compounds.
• These are polar compounds since their molecule acquires polarity due to the formation of ions by
electron transfer
 Characteristics of ionic compounds
1. They consist of oppositely charged ions held together by electrostatic forces of
attraction.
2. They are generally soluble in water and insoluble in organic solvents.
3. Due to the powerful electrostatic force between the ions in the crystals, considerable
amount of energy is required to separate the molecules from each other. Hence they
have high melting and boiling points.
4. When dissolved in water or in the molten state, they conduct electricity because the
binding forces in the crystal lattice are weakened.
5. They are crystalline compounds.
 COVALENT BOND
• Bond is formed by sharing of one or more electron pairs between the atoms
• Each atom achieves stability by attaining their octet or duplet in their outermost shell.
• The electrons for pair formation are contributed equally by the two participating atoms
and become their common property.
• There is no transfer of electrons and ions are not formed, the covalent linkage is also
called non-ionised linkage
 Polar and non-polar character
• In homonuclear diatomic molecules like H2 and Cl2, the sharing of electron
pair is equal between the two atoms and such a bond is called as a non-polar
covalent bond
• In hetero atomic molecules like HF or HCl, the sharing of electron pair is
unequal because, atom that attracts the electrons more strongly develops a
partial negative charge; and the other atom develops a partial positive
charge. For HCl this can be represented as: H δ+ ---- Cl δ-
 Characteristics of covalent compounds
1. The atoms in a covalent molecule are firmly held together by the shared pair of
electrons and hence covalent compounds do not dissociate or conduct electricity
when put in water or in the molten state.
2. Covalent compounds are generally insoluble in water and soluble in organic
solvents.
3. If a covalent molecule is non polar then it won’t have an external field of force.
Hence it would have low melting and boiling point.
4. Normally, covalent compounds are liquids or gases at room temperature.
However, covalent compounds with high molecular weights can exist as solids too.
 Why are Covalent compounds liquids or gases at room
temperature?

• There exist between Molecules of gases and liquids

some Forces of attraction.

• Some forces may be strong other forces may be weak.

• It’s these forces of attraction

that ultimately determine

how easy or difficult it is for

Gases to coalesce into Liquids

and liquids to solidify into

solids.

• These forces of attraction will,

for example, determine

boiling point of a liquid.

 What are these forces of attraction?
For gases and liquids these forces are of two types:

• Intermolecular - between molecules

• Intramolecular - within the molecule

• Intramolecular forces involve the formation of true chemical bonds

 Intramolecular forces vs. intermolecular forces
• Intramolecular forces of attraction are much stronger than the

intermolecular forces, because intramoleculear forces are the bonding

forces.

• Intramolecular forces are about 30 – 400 times stronger

• Intermolecular forces of attraction are also known as the Van der Waals

forces

• There are different types of intermolecular or Van der Waals forces of

attraction that exist between molecules of different types

 Three types of intermolecular forces

1. London Dispersion force

2. Dipole-Dipole force

3. Hydrogen bond
• Intermolecular forces are much weaker than
intramolecular (i.e. chemical bonding) forces
• Intermolecular forces also vary in strength from one
another:
• Dispersion…….Weakest (<1 Kcal)
Dipole-dipole ……. Stronger (2-5 Kcal)
Hydrogen bond ……. The Strongest (12-16 Kcal)
(for comparison, a true covalent bond is about 400Kcal)
Intermolecular forces hold molecules together in the Solid &
Liquid phase & Allow gases to condense on cooling.

• They also prevent instantaneous

evaporation from occurring.
• Strong Attractive forces between
molecules also make Vaporization
(L  G) phase changes more
difficult.
 Dispersion Forces
• Dispersion forces, the weakest intermolecular forces, are sometimes
also called the LONDON Dispersion Forces or induced dipole forces

• They result when there is a momentary shift in the electron density

within the molecules electron cloud

This intermolecular force is the predominant force for non-polar compounds

Non-polar molecules (no dipole formation) Polar molecules (Formation of

Temporary Dipoles)
Non-polar compounds are molecules that do not have a charge
distribution within the Molecule.

• Hence dipole-dipole interactions don’t exist in such

molecules
 The partial positive
positive and partial
negative centres line
up to give dipole-
dipole attractions
between molecules

δ -δ+ δ -δ+ δ- δ+ δ -δ+

• From fluorine to iodine, the electrons are further away from the nuclei so the electron clouds can more
easily distort.
• The larger the molecule the more easily δ charges develop. The London dispersion forces become
progressively stronger.
Non-polar compounds are molecules that do not have a permanent charge
distribution within the molecule.

• Molecules that have an even electron distribution are typically:

• 1) single atoms, or 2) molecules of the same element, or
3) hydrocarbons, or 4) symmetrical molecules
• For example: Ne, Kr, H2, O2, N2, S8, C3H8, CCl4, CO2
20
• Induced Dipole forces become stronger the larger the Atom or Molecule.

• Larger electron clouds are easier to deform

• One might expect the boiling pt. of compounds to be low for compounds
that interact by this type of force. Because the minimal force holding these
Molecules together Allow them to move readily from the liquid Phase into
the gas phase. Or even from the solid phase to gas phase - like I2
 CH4 C8H18
Smaller molecule Larger molecule
• If molecules have High boiling point (BP) they will have Low Vap
Pressure (VP) (and conversely Low boiling point means High VP)
• Since dispersion forces increase with increasing molecular weight
the Trend for non-polar compounds is… increasing BP with
increasing MW.
• This trend is also true with melting points (mp)/freezing points
(fp); as MW increases so does mp/fp)

Low MW Higher MW

Low BP Higher BP
Low dispersion force higher dispersion force

Let’s look at some bp data…

Which member of each pair should have the higher B.P. (and thus the
stronger Induced dipole)

1. N2, O2
O2 – Higher MW B.P: O2 -183.0˚C / N2 -195.6 ˚C
larger molecule

2. Ne, Kr
Kr - Higher MW B.P: Kr -152.9˚C / Ne -245.9˚C
Larger Atom

3. F2, Cl2
Cl2 – Higher MW B.P: Cl2 -34.6˚C / F2 -187˚C
Larger Molecule

4. C3H8 (propane), C4H10 (butane)

Butane (larger) B.P: C4H10 -0.5 C / C3H8 -42.1 C
M.P: -134.4 C -187.7 C
 Dipole- Dipole Forces
• Molecules that have permanent dipoles are said to be Polar.
• What does it mean to be a polar molecule?
• One area is always positive and another part of the
molecule is always negative
• An example of a polar molecule is HCl
Dipole- Dipole forces are stronger than London dispersion

forces (<1 Kcal vs. 2-5 Kcal)

- In this intermolecular force

Dipoles are always present

as opposed to constantly

forming and reforming

dipoles in weaker dispersion

force molecules
 Hydrogen Bond Forces
• The hydrogen bond is a special form of the Dipole-Dipole
force, its not really a true chemical bond.
- It is the strongest intermolecular force (12-16 Kcal)
- It is much stronger than either Dipole-Dipole Or London
Dispersion forces.
• However, It can ONLY exist when a Hydrogen atom is
present in the molecule AND it’s bonded to …
- Either a N, O, or F atom also present in the same molecule.
• In all compounds that form H-bonds
H F
the Hydrogen atom is ALWAYS the + -

Positive Dipole.

• O, F, or N is ALWAYS the negative

dipole +

• As one molecule approaches another

-
the positive Hydrogen aligns with the

negative O, F, or N.
Water Alignment during formation of the H-Bond

Positive aligns with negative

• Compounds that form Hydrogen bonds take a lot more energy to
move molecules from the liquid phase into the gas phase.
• Molecules of similar molecular weight without the ability to form H-
bonds have lower B.P.

H-bonding compound Molar Mass B.P. ⁰C

Yes H2O 18 + 100
Yes NH3 17 - 33
No CH4 16 - 164
 Types of Hydrogen bonding
There are two types of H-bonds, and it is classified as the following:
1. Intermolecular hydrogen bonding – This type of bond formation occurs between the
different molecules of same or different compounds. For example- p-nitro phenol.

2. Intramolecular hydrogen bonding – This type of bond

formation occurs when the hydrogen atom lies in between the
two electronegative elements present in the same molecule.
For example- o-nitro phenol
 CO-ORDINATE COVALENT BOND or DATIVE BOND
• Special type of covalent bond
• The atom which donates the electron pair is called as donor and the other atom which
does not contribute an electron towards the shared electron pair is called acceptor.
• A co-ordinate bond is usually represented by an arrow pointing from the donor to the
acceptor atom.
• Bond always renders the molecule polar, it is also called semi polar bond
• Compounds containing one or more of such co-ordinate bonds in their molecules are
often termed co-ordination compounds
 Characteristics of co-ordinate compounds

1. The co-ordinate bond is rigid and directional and hence provides opportunity for
exhibiting stereoisomerism of molecules.
2. These compounds are generally insoluble in water and soluble in organic solvents.
3. These compounds have relatively higher melting and boiling points than those of
covalent compounds and lower than those of electrovalent compounds.
4. The co-ordinate linkage being partly covalent in nature, the atoms are firmly held
by electrons and hence these compounds do not dissociate when placed in water
or melted.
5. The co-ordinate compounds are stable like covalent compounds.
 Introduction to co-ordination chemistry
• If an ion is composed of two or more species, the resultant ion is called complex ion and
the corresponding compound is called complex compound.
• It usually consists of a positive metal ion and a number of electron rich ligands which
can be anions or neutral molecules. These ligands form co-ordinate bonds with the
electron deficient metal ion.
• Number of ligands attached to the central metal ion or the no. of co-ordination bonds
formed with the central metal ion is called as co-ordination number
• The central metal cation is a lewis acid and the ligand is a lewis base
Example K4 [Fe(CN)6] is a complex compound where,
[Fe(CN)6]4- is complex anion denoted by square bracket
Fe+2 is the central metal cation and 6 CN- are ligands. Thus, 6 is the co-ordination number of Fe+2
• The central metal ion could be linked to two, three, four or even upto six ligands in the molecule.
• Ligands may be anions such as, F-, Cl-, CN-, OH-, I- and neutral molecules with lone pair of electrons such
as, H2:O:, :NH3.
• When an anion acts as a ligand, it losses its electrovalent character and gets attached to the central
metal ion through a non-ionisable linkage.

Central metal ion Ligands

• The charge on the complex ion is always the sum of the charges on the individual components.
• The complex compound may have a positive, negative or zero charge.
• Example: When Co3+ ions react with ammonia, the Co3+ ion accepts pairs of nonbonding electrons
from six NH3 ligands as shown in the figure below.

• The Co3+ ion is an electron-pair acceptor, or Lewis acid, because it has empty orbitals that can be used to
hold the accepted pairs of electrons. The configuration of the Co3+ ion as follows.

Co: [Ar] 3d7 4s2 4p0

Co3+: [Ar] 3d6 4s0 4p0
• There is place in the empty shells of this ion for 12 more electrons. Thus six NH3 ligands can contribute 12
electrons and combine with Co3+.
• In the formation of the co-ordination sphere, the number of ligands surrounding the central metal ion are
such that, the ion releases most energy and becomes most energetically stable.
 Classification of Ligands
On the basis of co-ordinate bonds ligands can be divided in to different categories:
1. Monodentate ligands: Any ligand donating one pair of electron is called monodentate ligands, examples,
:NH3, H2:O:, C:N-

2. Bidentate ligands: Any ligand donating two pairs of electron is called bidentate ligands, examples,

Ethylene diamine Oxalate ion

3. Tridentate ligands: Any ligand donating three pairs of electron is called tridentate ligands, examples

Bisethylene triamine

4. Polydentate ligands: Any ligand donating more than three pairs of electron is called polydentate ligand,
example

Ethylene diamine tetra acetic acid (EDTA)

The donor atoms in EDTA4- are the two N atoms, and the four, negatively charged O atoms.
 Magnetism of Coordination Compounds
• An interesting characteristic of transition metals is their ability to form magnets.
• Metal complexes that have unpaired electrons (high spin) are magnetic
(paramagnetic – attraction to a magnetic field).
• Metal complexes that have paired electrons (low spin) are non-magnetic
(diamagnetic – no attraction or weak repulsion to a magnetic field).
• Since the last electrons reside in the d orbitals, this magnetism must be due to
having unpaired d electrons.
• Considering only monometallic complexes, unpaired electrons arise because the
complex has an odd number of electrons or because electron pairing is
destabilized.
 Magnetism of Coordination Compounds
• For example, the Ti(III) ion has one d electron and must be (weakly) paramagnetic,

regardless of the geometry or the nature of the ligands.

• However, the Ti(II) ion with two d-electrons, sometimes forms complexes with two

unpaired electrons and sometimes forms complexes with no unpaired electrons.

• Another factor that plays a key role in whether a transition metal complex is high-

or low-spin is the nature of the ligands.

• The d orbital energy splitting is influenced by how strongly the ligand interacts with

the metal.
 Magnetism of Coordination Compounds
• Ligands that interact only weakly produce small difference between the d orbital

energy levels, whereas ligands that interact strongly produce a large difference

between in d orbital energy levels.

• The spectrochemical series is a list of ligands based on the strength of their

interaction with metal ions.

• The spectrochemical series is often listed, from weaker to stronger ligands as follows:

• I− < Br− < S2− < SCN− < Cl− < NO3− < N3− < F− < OH− < C2O42− < H2O < NCS− < CH3CN < py

< NH3 < en < bipy < phen < NO2− < PPh3 < CN− < CO
 Magnetism of Coordination Compounds
• For example, Fe prefers to exist as Fe3+ and is known to have a coordination

number of six. Since the configuration of Fe3+ has five d electrons, we would

expect to see five unpaired spins in complexes with the central atom Fe.

• This is true for [FeF6]3−

• However, [Fe(CN)6]3− only has one unpaired electron, making it a weaker magnet.

This trend can be explained based on the properties of the ligands.

 Magnetism of Coordination Compounds
• Thus, based on the spectrochemical series, we expect CN− ligands to have a

stronger electric field than that of F− ligands, so the energy differences in the d-

orbitals would be greater for the cyanide complex.

Pairing energy > energy difference Pairing energy < energy difference
between split d-orbitals between the split d-orbitals
High spin Low spin
(paramagnetic) (diamagnetic)
 Magnetism of Coordination Compounds
• To conclude:

• For a strong field ligand, the energy difference between the split d-orbitals is

larger, the e─ splitting energy is more than the e─ pairing energy, therefore the

electrons will pair up; resulting in a low-spin diamagnetic complex

• For a weak field ligand, the energy difference between the split d-orbitals is

smaller, the e─ splitting energy is less than the e─ pairing energy, therefore the

electrons will split (i.e. wont pair up); resulting in a high-spin paramagnetic

complex.