18 Electron Rule, Pi

Bonding, Sigma
Bonding
Prepared By: Elvinjan J. Acuña
 Objectives
At the end of the lesson, you should be able to:
1. describe 18 electron rule, its applications and
limitations;
2. be aware of the transition metal complexes that obey
or do not obey the 18 Electron Rule;
3. create a compound which sigma and pi bonding are
applied; and
4. count the number of pi bond and sigma bond in a
compound.
 Table of contents
01 02 03
HISTORY OF 18 ELECTRON RULE
18 ELECTRON LIMITATIONS AND
18 ELECTRON RULE
RULE APPLICATIONS

04 05
SIGMA PI BONDING
BONDING
 HISTORY OF 18 ELECTRON
RULE
⮚ 18 electron rule was first proposed by
the American chemist, Irving Langmuir.
He proposed this rule in order to extend
the Lewis static-atom model further
than Argon in the periodic table.

⮚ the 18 electron rule is more like octet

rule which can be applied to the whole
group with the same numerical value. Irving Langmuir(1881 – 1957)
 WHAT IS 18 ELECTRON
RULE?

The 18 Electron Rule is a useful tool to predict the structure and reactivity
of organometallic complexes.

The 18 Electron Rule is similar to the octet and duplet rules, as it is used to
predict stability.
 WHAT IS 18 ELECTRON
RULE?
The 18 electron rule states that: thermodynamically stable transition
metal compounds contain 18 valence electrons comprising of the
metal d electrons plus the electrons supplied by the metal bound
ligands.

This rule was proposed in order to explain the stability of transition metals
and the organometallic compounds which they form.The law is based on
the fact that, in the valence shell of transition elements the total number of
electrons is 2 s electrons, 6 p electrons and 10 d electrons making a total of
18 electrons.
WHAT IS 18 ELECTRON
RULE?
Examples of organometallic compound
obeying 18 e- rule
 How to count valence electron of
transition elements?

NEUTRAL METHOD IONIC METHOD

We first arrive at the
Metal is taken as in zero
oxidation state of the metal
oxidation state for counting
by considering the number of
purpose
anionic ligands present and
overall charge of the
complex
Fe(C5H5)2
 How to count valence electron of
transition elements?
Steps for ionic counting method:
1. Determine the overall charge of the metal complex.
2. Identify the charges of the ligands, and the numbers of e-s they
donate.
3. Determine the number of valence electrons of the metal center, so
that the oxidation state of the metal and charges of the ligands balance
the overall charge of the complex. (e- count of metal center = Metal
atom group number + ∑(charges of ionic ligands) – overall charge of
the complex)
4. If metal-metal bond is present, one bond counts for one electron for
each metal atom.
5. Add up the electron count of the metal center and the ligands.
 Ligand Covalent Ionic Charge

H 1 2 (H-) -1

Cl, Br, I 1 2 (X-) -1

OH, OR 1 2 (OH-,OR-) -1

CN 1 2 (CN-) -1

CH3, CR3 1 2 (CH3-,CR3-) -1

NO (bent M-N-
1 2 (NO-) -1
O)
NO (linear M-N-
3 2 (NO+) +1
O)
CO, PR3 2 2 0

NH3, H2O 2 2 0

=CRR' (carbene) 2 2 0
 Ligand Covalent Ionic Charge
H2C=CH2 (ethylene) 2 2 0

CNR 2 2 0

=O, =S 2 4 (O2-, S2-) -2

η3-C3H5 (π-allyl) 3 2 (C3H5+) +1

≡CR (carbyne) 3 3 0

≡N 3 6 (N3-) -3

en (Ethylenediamine) 4 4 0

bipy (Bipyridine) 4 4 0

butadiene 4 4 0
η5 -
5 6 (C5H5-) -1
C5H5 (cyclopentadienyl)
 [Co(NH3)6]Cl3
Overall charge: 3+
Charge on ligands: 0
Number of e- ligands donate: 2x 6
Valence e- of Cobalt: 9
Cobalt ion d e-: 6

Total number of e- = (2x6)+6

= 18 e-
Mn2(CO)10

Overall charge: 0
Charge on ligands: 0
Number of e- ligands donate: 2x5
Valence e- of Mn: 7
Metal-Metal bond: 1
Total number of e- = (2x5)+7+1
= 18 e-
Transition metal organometallic compounds mainly belong to
any of the three categories:
Class I complexes for which the number of valence electrons
do not obey the 18 VE rule.
Class II complexes for which the number of valence electrons
do not exceed 18.
Class III complexes for which the valence electrons exactly
obey the 18 VE rule.
Limitations of 18 Electron Rule

1.16 Electron Compounds

2.Bulky Ligands
3.High Spin Compounds
4.Higher Electron Compounds
5.𝛑-donating Ligands
6.Other Block Elements
7.Multiple Metal Atoms
Applications of 18 Electron Rule

1. Predicts the stability of various organometallic

compounds.
2. Predicts the reactivity of transition elements.
3. Used to predict and refine the formulas of
various complex compounds, especially
organometallic compounds.
4. Used to predict the existence of metal-metal
bonds in complexes.
SIGMA AND PI
BONDING
Sigma and pi bonds are types of
covalent bonds that differ in the
overlapping of atomic orbitals
 Sigma (σ) Bond
This type of covalent bond is formed by
head-on positive (same phase) overlap
of atomic orbitals along the internuclear
axis. 

The electrons participating in a σ bond
are commonly referred to as σ
electrons.

Generally, all single bonds are sigma

bonds. They can be formed via the
following combinations of atomic
orbitals.
 Sigma Bond
Sigma can be formed via the following combinations of atomic
orbitals:

1. s-s Overlapping
In this kind of overlapping, one ‘s’ orbital from each participating
atom undergoes head-on overlapping along the internuclear
axis
 Sigma Bond

1. s-s Overlapping
 Sigma Bond
2. s-p Overlapping
Here, one half filed s orbital
overlaps with one half-filled p
orbitals along the internuclear
axis, forming a covalent bond. 

3. p-p overlapping
In this condition, one half-
filled p orbital from each
participating atom
undergoes head-on
overlapping along the
internuclear axis.
 Pi (π) Bonding
Pi bonds are formed by the sidewise positive (same phase)
overlap of atomic orbitals along a direction perpendicular to
the internuclear axis. During the formation of π bonds, the
axes of the atomic orbitals are parallel to each other whereas
the overlapping is perpendicular to the internuclear axis.
Differences between Sigma (σ) Pi (π)
Bonding
Sigma Bond Pi Bond

The overlapping orbitals The overlapping orbitals

can be pure or hybrid must be unhybridized
These bonds are strong These bonds are relatively
and have high bond weak.
energies.
Can exist independently Must exist along with a
sigma bond.
Has an impact on the Has no role in determining
shape of molecules the shape of molecules
Counting number of Sigma (σ) Pi (π) Bonds

1 single bond = 1 sigma bond

1 double bond = 1 sigma bond and one pi bond
1 triple bond = 1 sigma bond and 2 pi bond
Counting number of Sigma (σ) Pi (π) Bonds

C2H4
5 sigma bonds
1 pi bond
Counting number of Sigma (σ) Pi (π) Bonds

C2H2
3 sigma bonds
2 pi bonds
Counting number of Sigma (σ) Pi (π) Bonds

CH2O
3 sigma bonds
1 pi bond
Counting number of Sigma (σ) Pi (π) Bonds

SO2Cl2
4 sigma bonds
2 pi bonds
 ANY
QUESTIONS?
THANK YOU!