Chapter 6, 7

Chemical Bonding and Molecular Structure

 Chemical bond is the force that holds atoms together in

a chemical compound.
 There are two types of chemical bonding:
 Covalent bonding- electrons are shared between atoms
in a molecule or polyatomic ion, and
 Ionic bonding- positively and negatively charged ions
are held together by electrostatic forces.

1
 Lewis Dot Symbols
 Lewis dot symbol consists of the symbol of an element and one dot for
each valence electron in an atom of the element.

2
 The Ionic Bond
Ionic bond: the electrostatic force that holds ions together in an
ionic compound.
Li + F Li+ F -
1s22s1 1s22s22p5 1s2 1s22s22p6
[He] [Ne]
Li Li+ + e-

LiF F F -
e- +

Li+ + F - Li+ F -

3
 Electrostatic (Lattice) Energy
Lattice energy (U) is the energy required to completely separate
one mole of a solid ionic compound into gaseous ions.
Lattice energy cannot be measured directly. However, if we know
the structure and composition of an ionic compound, we can
calculate the compound’s lattice energy by using Coulomb’s law

E is the potential energy

Q+ is the charge on the cation

E = k Q+ Q- Q- is the charge on the anion

r r is the distance between the ions
Compound Lattice Energy
(kJ/mol)
Lattice energy increases MgF2 2957 Q: +2,-1
as Q increases and/or MgO 3938 Q: +2,-2
as r decreases. 4
Example: Calculate the amount of energy released when 1
mol of gaseous Li+F− ion pairs is formed from the separated
ions. The observed internuclear distance in the gas phase is
156 pm (Proportionality constant, k = 8.999 × 109 J·m/C2, Q1
= +1(1.6022 × 10−19 C) and Q2 = −1(1.6022 × 10−19 C).
Solution: the energy released in the formation of a single ion pair
E=k
the energy released per mole
E = (k ) x NA, NA = Avogadro’s Number = 6.022x1023
= (8.999 × 109 J·m/C2 x 1.6022 × 10−19 C x -1.6022 × 10−19 C x
6.022x1023)/156 x10-12 m
= 891 kJ/mol
5
The Born-Haber Cycle for Determining Lattice Energies
 It is also possible to determine lattice energy indirectly, by
assuming that the formation of an ionic compound takes
place in a series of steps.
 This procedure, known as the Born-Haber cycle, relates
lattice energies of ionic compounds to ionization
energies, electron affinities, and other atomic and
molecular properties.
 It is based on Hess’s law.
 Consider the reaction between lithium and fluorine:

 The standard enthalpy change for this reaction is -594.1

kJ/mol.
6
Five steps in determining lattice energy:
1. Convert solid lithium to lithium vapour (the direct conversion of
a solid to a gas is called sublimation):

The energy of sublimation for lithium is 155.2 KJ/mol.

2. Dissociate mole of F2 gas into separate gaseous F atoms:

The energy needed to break the bonds in 1 mole of F2 molecules

is 150.6 KJ. Here we are breaking the bonds in half a mole of F2,
so the enthalpy change is 150.6/2, or 75.3 KJ.
7
3. Ionize 1 mole of gaseous Li atoms

This process corresponds to the first ionization of lithium.

4. Add 1 mole of electron to 1 mole of gaseous F atom. The energy
change for this process is just the opposite of electron affinity.

5. Combine 1 mole of gaseous Li+ and 1 mole of F- to form 1 mole of

solid LiF:

The reverse of step 5 defines the lattice energy of LiF.

8
Thus, the lattice energy must have the same magnitude as ∆Ho5
but an opposite sign.

According to Hess’s law, we can write

and the lattice energy of LiF is +1017 kJ/mol. 9

The Born-Haber cycle for the formation of 1 mole of solid LiF

10
A covalent bond is a chemical bond in which two or more
electrons are shared by two atoms.

Why should two atoms share electrons?

F + F F F
7e- 7e- 8e- 8e-

Lewis structure of F2

single covalent bond lone pairs F F lone pairs

single covalent bond

lone pairs F F lone pairs

11
 Lewis structure of water single covalent bonds

H + O + H H O H or H O H
2e-8e-2e-

Double bond – two atoms share two pairs of electrons

O C O or O C O
double bonds 8e- 8e- 8e- double bonds

Triple bond – two atoms share three pairs of electrons

N N or N N
8e- 8e-
triple bond
12
triple bond
 Lengths of Covalent Bonds

Bond Lengths
Triple bond < Double Bond < Single Bond 13
 Electronegativity
Polar covalent bond or polar bond is a covalent bond with greater
electron density around one of the two atoms

electron rich
electron poor
region
region e- poor e- rich

H F H F
d+ d-

14
Electronegativity is the ability of an atom to attract
electrons toward itself in a chemical bond.

Electron Affinity - measurable, Cl is highest

X (g) + e- X-(g)

Electronegativity - relative, F is highest

15
The Electronegativity of Common Elements

16
Variation of Electronegativity with Atomic Number

17
Classification of bonds by difference in electronegativity

Difference Bond Type

0 Covalent
2 Ionic
0 < and <2 Polar Covalent

Increasing difference in electronegativity

Covalent Polar Covalent Ionic

share e- partial transfer of e- transfer e-

18
Example:
Classify the following bonds as ionic, polar covalent, or
covalent: The bond in CsCl; the bond in H2S; and the NN bond
in H2NNH2.

Cs – 0.7 Cl – 3.0 3.0 – 0.7 = 2.3 Ionic

H – 2.1 S – 2.5 2.5 – 2.1 = 0.4 Polar Covalent

N – 3.0 N – 3.0 3.0 – 3.0 = 0 Covalent

19
 Writing Lewis Structures

1. Draw skeletal structure of compound showing what

atoms are bonded to each other. Put least
electronegative element in the center.

2. Count total number of valence e-. Add 1 for each

negative charge. Subtract 1 for each positive charge.

3. Complete an octet for all atoms except hydrogen

4. If structure contains too many electrons, form double

and triple bonds on central atom as needed.

20
Write the Lewis structure of nitrogen trifluoride (NF3)
Step 1 – N is less electronegative than F, put N in center
Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 – Draw single bonds between N and F atoms and complete
octets on N and F atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?

3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

F N F

21
 Write the Lewis structure of the carbonate ion (CO32-)
Step 1 – C is less electronegative than O, put C in center
Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4)
-2 charge = 2e-
4 + (3 x 6) + 2 = 24 valence electrons
Step 3 – Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e-

2 single bonds (2x2) = 4

1 double bond = 4
O C O 8 lone pairs (8x2) = 16
Total = 24
O 22
Two possible skeletal structures of formaldehyde (CH2O)

H
H C O H C O
H
 An atom’s formal charge is the difference between the
number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
Formal charge Total number Total number
Total number

( )
on an atom in of valence 1
a Lewis = electrons in - of nonbonding
electrons
- 2
of bonding
electrons
structure
the free atom

 The sum of the formal charges of the atoms in a

molecule or ion must equal the charge on the molecule
or ion. 23
 -1 +1 C – 4 e- 2 single bonds (2x2) = 4
H C O H O – 6 e- 1 double bond = 4
2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12

Formal charge Total number

Total number Total number
( )
on an atom in of valence 1
electrons in - -
a Lewis
= of nonbonding of bonding
electrons 2 electrons
structure the free atom

Formal charge
on C
= 4 -2 - ½ x 6 = -1

Formal charge
on O
= 6 -2 - ½ x 6 = +1

24
 H 0 0 C – 4 e- 2 single bonds (2x2) = 4
C O O – 6 e- 1 double bond = 4
H 2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12

Formal charge Total number

Total number Total number
( )
on an atom in of valence 1
electrons in - -
a Lewis
= of nonbonding of bonding
electrons 2 electrons
structure the free atom

Formal charge
on C
= 4 - 0 -½ x 8 = 0

Formal charge
on O
= 6 -4 - ½ x 4 = 0

25
Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.
Which is the most likely Lewis structure for CH2O?

-1 +1 H 0 0
H C O H C O
H
26
A resonance structure is one of two or more Lewis structures
for a single molecule that cannot be represented accurately by
only one Lewis structure.

+ - - +
O O O O O O

What are the resonance structures of the

carbonate (CO32-) ion?

- - - -
O C O O C O O C O

O O O
- - 27
 Exceptions to the Octet Rule

The Incomplete Octet

Be – 2e-
BeH2 2H – 2x1e- H Be H
4e-

B – 3e- 3 single bonds (3x2) = 6

3F – 3x7e- F B F
BF3 9 lone pairs (9x2) = 18
24e- Total = 24
F

28
 Exceptions to the Octet Rule

Odd-Electron Molecules

N – 5e-
NO O – 6e- N O
11e-

The Expanded Octet (central atom with principal quantum number n > 2)

F
F F
S – 6e- 6 single bonds (6x2) = 12
SF6 6F – 42e- S 18 lone pairs (18x2) = 36
48e- Total = 48
F F
F
29
The enthalpy change required to break a particular bond in one
mole of gaseous molecules is the bond enthalpy.

Bond Enthalpy
H2 (g) H (g) + H (g) DH0 = 436.4 kJ
Cl2 (g) Cl (g) + Cl (g) DH0 = 242.7 kJ
HCl (g) H (g) + Cl (g) DH0 = 431.9 kJ
O2 (g) O (g) + O (g) DH0 = 498.7 kJ O O
N2 (g) N (g) + N (g) DH0 = 941.4 kJ N N

Bond Enthalpies
Single bond < Double bond < Triple bond
30
 Bond Enthalpies (BE) and Enthalpy changes in reactions
Imagine reaction proceeding by breaking all bonds in the reactants and
then using the gaseous atoms to form all the bonds in the products.

DH0 = total energy input – total energy released

= SBE(reactants) – SBE(products)

exothermic 31
endothermic
Example: Estimate the enthalpy change for the combustion of
hydrogen gas:

Where bond enthalpy of (H – H) = 436.4 kJ/mol,

(O = O) = 498.7 kJ/mol, (O – H) = 460 kJ/mol

32
Molecular Geometry and Hybridization of
Atomic Orbitals

 Molecular geometry is the three-dimensional

arrangement of atoms in a molecule.
 A molecule’s geometry affects its physical and
chemical properties, such as melting point, boiling
point, density, and the types of reactions it undergoes.
 There is a simple procedure that enables us to predict
the overall geometry of a molecule or ion if we know
the number of electrons surrounding a central atom in
its Lewis structure. 33
Valence-shell electron-pair repulsion
(VSEPR) model
 Accounts for the geometric arrangements of
electron pairs around a central atom in terms
of the electrostatic repulsion between electron
pairs.
 To predict the geometry of molecules (and
ions), it is convenient to divide molecules into
two categories, according to whether or not
the central atom has lone pairs.

34
Molecules in Which the Central Atom Has No
Lone Pairs
 For simplicity consider molecules that contain atoms of
only two elements, A and B, of which A is the central
atom.
 These molecules have the general formula ABx, where x
is an integer 2, 3, . . . . (If x = 1, we have the diatomic
molecule AB, which is linear by definition.) In the vast
majority of cases, x is between 2 and 6.
 As a result of mutual repulsion, the electron pairs stay as
far from one another as possible and the geometry of
molecules with the formulas AB2, AB3, AB4, AB5, and AB6
are given in the table below. 35
36
Molecules in which the central Atom has one
or more lone pairs
Postulates of VSEPR Theory
(1) The shape of the molecule is determined by repulsion
between all of the electron pairs present in the valence shell.
(2) A lone pair of electrons takes up more space round the
central atom than a bond pair. The repulsive interactions
decrease in the order:
LP-LP > LP-BP > BP-BP
(3) The magnitude of repulsion between bonding pairs of
electrons depends on the electronegativity difference between
the central atom and the other atoms.
(4) Double bonds cause more repulsion than single bonds,
37
and triple bonds cause more repulsion than a double bond.
38
39
Guidelines for Applying the VSEPR Model

Example:
Use the VSEPR model to predict the geometry of the
following molecules and ions:
(a) AsH3
(b) OF2
(c) AlCl4-
(d) I3-
40
(e) C2H4
 Dipole Moments
A quantitative measure of the polarity of a bond is its dipole
moment (µ), which is the product of the charge Q and the distance r
between the charges:
µ=Qxr
Q refers only to the magnitude of the charge and not to its sign, so µ
is always positive.
Diatomic molecules containing atoms of different elements (for
example, HCl, CO, and NO) have dipole moments and are called
polar molecules. Diatomic molecules containing atoms of the same
element (for example, H2, O2, and F2) are examples of nonpolar
molecules because they do not have dipole moments.

41
Even if polar bonds are present, the molecule will not
necessarily have a dipole moment.

The arrows show the shift of electron density from the

less electronegative carbon atom to the more
electronegative oxygen atom.

42
 Dipole moments can be used to distinguish between
molecules that have the same formula but different
structures.
 Because cis-dichloroethylene is a polar molecule but
trans-dichloroethylene is not, they can readily be
distinguished by a dipole moment measurement.

43
Valence Bond Theory and Molecular orbital Theory
 Valence bond (VB) theory assumes that the electrons in
a molecule occupy atomic orbitals of the individual atoms.
Molecular orbital (MO) theory assumes the formation of
molecular orbitals from the atomic orbitals.
 Valence bond theory states that a stable molecule forms
from reacting atoms when the potential energy of the
system has decreased to a minimum. In the framework of
valence bond theory, the covalent H—H bond is formed by
the overlap of the two 1s orbitals in the H atoms. By
overlap, we mean that the two orbitals share a common
region in space.
44
Change in Potential Energy of Two Hydrogen Atoms
as a Function of Their Distance of Separation

45
Change in electron density as two hydrogen atoms
approach each other.

46
 The concept of overlapping atomic orbitals
applies equally well to diatomic molecules other
than H2. Thus, a stable F2 molecule forms when
the 2p orbitals (containing the unpaired electrons)
in the two F atoms overlap to form a covalent
bond.
 Similarly, the formation of the HF molecule can be
explained by the overlap of the 1s orbital in H
with the 2p orbital in F. In each case, VB theory
accounts for the changes in potential energy as
the distance between the reacting atoms
changes. 47
 Hybridization of Atomic Orbitals

 VB theory uses hypothetical hybrid orbitals, which are

atomic orbitals obtained when two or more non-
equivalent orbitals of the same atom combine in
preparation for covalent bond formation.

 Hybridization is the term applied to the mixing of

atomic orbitals in an atom (usually a central atom) to
generate a set of hybrid orbitals.

48
sp3 Hybridization
Consider the CH4 molecule. Focusing only on the valence
electrons, we can represent the orbital diagram of C as

promote (energetically excite) an electron from the 2s orbital to the

2p orbital:

Now there are four unpaired electrons on C that could form four
C—H bonds and four equivalent hybrid orbitals are generated by
mixing the 2s orbital and the three 2p orbitals:
The new orbitals are formed from
one s and three p orbitals, they are
called sp3 hybrid orbitals. 49
These four hybrid orbitals are directed toward the four corners of
a regular tetrahedron. Thus, CH4 has a tetrahedral shape, and
all the HCH angles are 109.5o.

50
sp2 Hybridization
Based on VSEPR, the BF3 (boron trifluoride) molecule has planar geometry.
Considering only the valence electrons, the orbital diagram of B is

Promoting a 2s electron to an empty 2p orbital:

Mixing the 2s orbital with the two 2p orbitals generates three sp2 hybrid orbitals:

Each of the BF bonds is formed by the overlap of a

boron sp2 hybrid orbital and fluorine 2p orbital. The
BF3 molecule is planar with all the FBF angles equal 51
to 120o.
sp Hybridization
The beryllium chloride (BeCl2) molecule is predicted to be linear by VSEPR.
The orbital diagram for the valence electrons in Be is

promote a 2s electron to a 2p orbital, resulting in

the 2s and 2p orbitals must be mixed, or hybridized, to form two equivalent sp

hybrid orbitals:

These two hybrid orbitals lie on the same line, the x-axis, so that the angle
between them is 180o. Each of the BeCl bonds is then formed by the overlap
of a Be sp hybrid orbital and a Cl 3p orbital, and the resulting BeCl2 molecule
52
has a linear geometry.
 Procedure for Hybridizing Atomic Orbitals
Hybridization simply extends Lewis theory and the VSEPR model.
To assign a suitable state of hybridization to the central atom in a
molecule, we must have some idea about the geometry of the
molecule. The steps are as follows:
1. Draw the Lewis structure of the molecule.
2. Predict the overall arrangement of the electron pairs (both
bonding pairs and lone pairs) using the VSEPR model.
3. Deduce the hybridization of the central atom by matching the
arrangement of the electron pairs with those of the hybrid orbitals.

53
Example:
Determine the hybridization state of the central atom in each of the
following molecules: (a) BeH2, (b) AlI3, and (c) PF3.

Describe the hybridization process and determine the molecular

geometry in each case.

draw Lewis structure use VSEPR to determine the determine the

electron pair arrangement hybridization state of
surrounding the central atom the central atom

54
How to predict the hybridization of the central atom?

1. Draw the Lewis structure of the molecule.

2. Count the number of lone pairs AND the number of
atoms bonded to the central atom
# of Lone Pairs
+
# of Bonded Atoms
Hybridization Examples
(electronic structure)
2 (linear) sp BeCl2

3 (trigonal planar) sp2 BF3

4 (tetrahedral) sp3 CH4, NH3, H2O

5 (trigonal bipyramidal) sp3d PCl5

6 (octahedral) sp3d2 SF6 55

 Hybridization of s, p, and d Orbitals
Consider the SF6 molecule as an example. The ground-state electron
configuration of S is [Ne]3s23p4:

Because the 3d level is quite close in energy to the 3s and 3p levels, we

can promote 3s and 3p electrons to two of the 3d orbitals:

Mixing the 3s, three 3p, and two 3d orbitals generates six sp3d2 hybrid orbitals:

The six S—F bonds are formed by the overlap of the hybrid orbitals of the S atom
56
with the 2p orbitals of the F atoms.
 Hybridization in Molecules Containing Double and Triple Bonds
Consider the ethylene molecule, C2H4, as an example. C2H4 contains a
carbon-carbon double bond and has planar geometry. Both the geometry
and the bonding can be understood if we assume that each carbon atom is
sp2- hybridized. Each carbon atom uses the three sp2 hybrid orbitals to
form two bonds with the two hydrogen 1s orbitals and one bond with the
sp2 hybrid orbital of the adjacent C atom. In addition, the two unhybridized
2pz orbitals of the C atoms form another bond by overlapping sideways.

57
Sigma bonds (σ bonds), covalent bonds formed by orbitals overlapping end-
to-end, with the electron density concentrated between the nuclei of the
bonding atoms.

Pi bond (π bond), which is defined as a covalent bond formed by sideways

overlapping orbitals with electron density concentrated above and below the
plane of the nuclei of the bonding atoms.

58
Another View of p Bonding in Ethylene, C2H4

59
sp Hybridization of Carbon

60
Bonding in Acetylene, C2H2

61
 Sigma (s) and Pi Bonds (p)

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many s and p bonds are in the acetic acid (vinegar)

molecule CH3COOH?

H
O

s bonds = 6 + 1 = 7
H C C O H
p bonds = 1
H
62
Describe the bonding in CH2O.

H
C O
H
C – 4 bonded atoms, 0 lone pairs
C – sp3
C – 3 bonded atoms, 0 lone pairs
C – sp2
C – 2 bonded atoms, 0 lone pairs
C – sp

63
 Molecular Orbital Theory
 Magnetic and other properties of molecules are
sometimes better explained by another quantum
mechanical approach called molecular orbital (MO)
theory.
 Molecular orbital theory describes covalent bonds in
terms of molecular orbitals, which result from interaction
of the atomic orbitals of the bonding atoms and are
associated with the entire molecule.
 The difference between a molecular orbital and an atomic
orbital is that an atomic orbital is associated with only one
atom.
64
 Bonding and Anti-bonding Molecular Orbitals
 According to MO theory, the overlap of the 1s orbitals of two
hydrogen atoms leads to the formation of two molecular orbitals: one
bonding molecular orbital and one anti-bonding molecular orbital.
 A bonding molecular orbital has lower energy and greater stability
than the atomic orbitals from which it was formed. An anti-bonding
molecular orbital has higher energy and lower stability than the
atomic orbitals from which it was formed. As the names “bonding”
and “anti-bonding” suggest, placing electrons in a bonding molecular
orbital yields a stable covalent bond, whereas placing electrons in an
anti-bonding molecular orbital results in an unstable bond.

65
Energy levels diagram of molecular orbitals in the H2 molecule

66
For p orbitals, the process is more complex because they can
interact with each other in two different ways. For example, two 2p
orbitals can approach each other end-to-end to produce a sigma
bonding and a sigma antibonding molecular orbital.

67
Alternatively, the two p orbitals can overlap sideways to generate a
bonding and an antibonding pi molecular orbital.

68
Molecular Orbital Configurations
Rules Governing Molecular Electron Configuration and Stability
1. The number of molecular orbitals formed is always equal to the number of
atomic orbitals combined.
2. The more stable the bonding molecular orbital, the less stable the
corresponding antibonding molecular orbital.
3. The filling of molecular orbitals proceeds from low to high energies.
4. Like an atomic orbital, each molecular orbital can accommodate up to two
electrons with opposite spins in accordance with the Pauli exclusion principle.
5. When electrons are added to molecular orbitals of the same energy, the most
stable arrangement is predicted by Hund’s rule; that is, electrons enter these
molecular orbitals with parallel spins.
6. The number of electrons in the molecular orbitals is equal to the sum of all the
electrons on the bonding atoms.
69
 Hydrogen and Helium Molecules
The σ1s and σ*1s orbitals can accommodate a maximum of four electrons. The total
number of electrons increases from one for H2 to four for He2. The Pauli exclusion
principle stipulates that each molecular orbital can accommodate a maximum of
two electrons with opposite spins.

Energy levels of the molecular orbitals in H2, H2+, He2+, and He2. 70
The bond order indicates the strength of a bond. Bond order of zero (or a negative
value) means the bond has no stability and the molecule cannot exist.
Consider H2, H2+, He2+, and He2. The electron configuration of H2+ is written as
(σ1s) 1. Bond order of H2+ is 1/2. Thus, we predict that the H2+ molecule may be a
stable species. The H2 molecule has two electrons and its electron configuration is
(σ1s) 2. Two electrons equal one full bond; therefore, the H2 molecule has a bond
order of one.
He2+ molecular ion has tree electrons and the first two electrons can be placed in σ 1s
orbital while the third electron placed in σ1s* orbital. The bond order is ½(2-1) =
1/2 and its electronic configuration is (σ1s) 2(σ1s*)1. The electronic configuration of
He2 is (σ1s) 2(σ1s*)2 and its bond order is ½(2-2) = 0. Hence, the molecule He 2 is
71
unstable.
 Homonuclear Diatomic Molecules of Second-Period Elements
Homonuclear diatomic molecules are diatomic molecules containing atoms
of the same elements. Consider the molecule Li2. The electronic
configuration of Li atom is 1s22s1. The molecular orbitals are formed by the
overlap of 1s and 2s orbitals.

72
The situation is more complex when the bonding also involves p orbitals. Two p
orbitals can form either a sigma bond or a pi bond. From three p orbitals for each
atom of a second-period element, one sigma and two pi molecular orbitals will
result from the constructive interaction. The sigma molecular orbital is formed by
the overlap of the 2px orbitals along the internuclear axis, that is, the x-axis. The
2py and 2pz orbitals are perpendicular to the x-axis, and they will overlap sideways
to give two pi molecular orbitals. The molecular orbitals are called σ 2px, π2py, and
π2pz orbitals, where the subscripts indicate which atomic orbitals take part in
forming the molecular orbitals.
Energy order of molecular orbitals increases as follow:

73
Example: Molecular orbital energy level diagram for the second-period
homonuclear diatomic molecules Li2, Be2, B2, C2, and N2
74
75
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.

Example: Benzene, C6H6

Delocalized p orbitals

76
Bonding in the Carbonate Ion, CO32-

77
 Coordination Compounds

Transition metals have a distinct tendency to form complex ions.

A coordination compound typically consists of a complex ion and

counter ion. The molecules or ions that surround the metal in a

complex ion are called ligands.

78
22.1
Oxidation States of the 1st Row Transition Metals
(most stable oxidation numbers are shown in red)
 The interactions between a metal atom and the ligands can be

thought of as Lewis acid-base reactions. Lewis base is a

substance capable of donating one or more electron pairs.

Ligands play the role of Lewis bases and a transition metal atom (in

either its neutral or positively charged state) acts as a Lewis acid,

accepting (and sharing) pairs of electrons from the Lewis bases.

Thus, the metal-ligand bonds are usually coordinate covalent bonds.

81
The atom in a ligand that is bound directly to the metal atom is

known as the donor atom. For example, nitrogen is the donor

atom in the [Cu(NH3)4]2+ complex ion. The coordination number

is defined as the number of donor atoms surrounding the central

metal atom. For example, the coordination number of Ag+ in

[Ag(NH3)2]+ is 2, that of Cu2+ in [Cu(NH3)4]2+ is 4, and that of Fe3+

in [Fe(CN)6]3+ is 6. Depending on the number of donor atoms

present, ligands are classified as monodentate, bidentate, 82or

83
Bidentate and polydentate ligands are also called chelating

agents. For example, in metal ethylenediamine complex cation

such as [Co(en)3]2+, each ethylenediamine molecule provides

two N donor atoms and is therefore a bidentate ligand.

84
 Oxidation Number of Metals in Coordination Compounds

The net charge of a complex ion is the sum of the charges on the central metal
atom and its surrounding ligands. In the [PtCl6]2- ion, for example, each chloride
ion has an oxidation number of -1, so the oxidation number of Pt must be +4. If
the ligands do not bear net charges, the oxidation number of the metal is equal to
the charge of the complex ion. Thus, in [Cu(NH3)4]2+ each NH3 is neutral, so the
oxidation number of Cu is +2.

Example: Specify the oxidation number of the central metal atom in each of the
following compounds: (a) [Ru(NH3)5(H2O)]Cl2, (b) [Cr(NH3)6](NO3)3, (c)

[Fe(CO)5], and (d) K4[Fe(CN)6].

85
Naming Coordination Compounds
The rules for naming coordination compounds are as follows:
1. The cation is named before the anion, as in other ionic compounds.
The rule holds regardless of whether the complex ion bears a net
positive or a negative charge. For example, in the K3[Fe(CN)6] and
[Co(NH3)4Cl2]Cl compound, we name the K+ and [Co(NH3)4Cl2]+
cations first, respectively.
2. Within a complex ion the ligands are named first, in alphabetical
order, and the metal ion is named last.
3. The names of anionic ligands end with the letter o, whereas a
neutral ligand is usually called by the name of the molecule. The
exceptions are H2O (aqua), CO (carbonyl), and NH3 (ammine).
86
4. When several ligands of a particular kind are present, we use the
Greek prefixes di-, tri-, tetra-, penta-, and hexa- to name them. If the
ligand itself contains a Greek prefix, we use the prefixes bis (2), tris
(3), and tetrakis (4) to indicate the number of ligands present. For
example, the ligand ethylenediamine already contains di; therefore, if
two such ligands are present the name is bis(ethylenediamine).
5. The oxidation number of the metal is written in Roman numerals
following the name of the metal. For example, the Roman numeral III
is used to indicate the +3 oxidation state of chromium in
[Cr(NH3)4Cl2]+, which is called tetraamminedichlorochromium(III)
ion.
6. If the complex is an anion, its name ends in -ate. For example, in
K4[Fe(CN)6] the anion [Fe(CN)6]4- is called hexacyanoferrate(II) ion.
Note that the Roman numeral II indicates the oxidation state of iron.
87
Table: Name of common ligands in coordination compounds

88
89
Example: Write the systematic names of the following coordination
compounds:
(a) Ni(CO)4, (b) NaAuF4, (c) K3[Fe(CN)6], (d) [Cr(en)3]Cl3.
Answer: (a) tetracarbonylnickel(0) or nickel tetracarbonyl, (b)
sodium tetrafluoroaurate(III), (c) potassium hexacyanoferrate(III)
or potassium ferricyanide,
(d) tris(ethylenediamine)chromium(III) chloride
Example: Write the formulas for the following compounds:
(a) pentaamminechlorocobalt(III) chloride,
(b) dichlorobis(ethylenediamine)platinum(IV) nitrate, (c) sodium
hexanitrocobaltate(III).
90
 Geometry of Coordination Compounds
Coordination Structure Example
Number
2 Linear [Ag(NH3)2]+, [CuCl2]-, [Au(CN)2]-

4 Tetrahedral [Zn(NH3)4]2+, [CoCl4]2-

4 Square planar [Pt(NH3)4]2+
6 Octahedral [Co(NH3)4Cl2]+

91
Bonding in Coordination Compounds: Crystal Field Theory

Crystal Field Theory accounts for both the color and magnetic
properties of many coordination compounds. Crystal field theory
explains the bonding in complex ions purely in terms of
electrostatic forces. In a complex ion, two types of electrostatic
interaction come into play. One is the attraction between the
positive metal ion and the negatively charged ligand or the
negatively charged end of a polar ligand. This is the force that
binds the ligands to the metal. The second type of interaction is
electrostatic repulsion between the lone pairs on the ligands and
the electrons in the d orbitals of the metals. 92
The crystal field splitting (∆) is the energy difference between

two sets of d orbitals in a metal atom when ligands are present.

The magnitude of ∆ depends on the metal and the nature of the

ligands: it has a direct effect on the color and magnetic properties

of complex ions. The best way to measure crystal field splitting

is to use spectroscopy to determine the wavelength at which light

is absorbed.

93
For a number of complexes, all having the same metal ion but different ligands, a

list of ligands arranged in increasing order of their abilities to split the d orbital

energy levels:

CO and CN- are called strong-field ligands, because they cause a large

splitting of the d orbital energy levels. The halide ions and hydroxide ion are

weak-field ligands, because they split the d orbitals to a lesser extent.

94
Figure: Crystal field splitting between d orbitals in an octahedral complex

95
Figure: Crystal field splitting between d orbitals in a tetrahedral complex.

96
Figure: Energy-level diagram for a square-planar complex.

97