The 18- electron Rule

Inorganic Chemistry-II
CHEM F241
Effective Atomic Number (EAN) Rule
❑ Initial efforts to account for the bonding in transition metal
complexes were laid by Sidgwick

❑ Ligands were considered as Lewis bases and metals in turn

behaved as Lewis acids

❑ Stability was related to attending the noble gas configuration

❑ EAN Rule: Sum of the electrons on the metal + electrons

donated from the ligands. Examples

❑ When EAN is equal to 36 (Kr), 54 (Xe) or 86 (Rn), the EAN Rule

is said to be obeyed.

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
The 18-electron Rule
✓ An alternative or more general version is the 18-electron Rule:
When a metal achieves an outershell configuration of ns2(n-1)d10np6
there will be 18 electrons in the valence orbitals with a closed and
stable configuration.

✓ Advantages:
▪ It is the same for all rows of the periodic table. No need to remember
a different EAN for each noble gas.
▪ The number is an easy one to remember.
▪ This rule is obeyed by a wider population of organometallic
compounds, especially those having carbonyls or nitrosyls.

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Applications of the 18-electron Rule
In general 18-electron rule is remarkably important in understanding the
structure, stability and property of an organometallic compound.
➢ Prediction of the number of metal-metal bonds/ formation of bridging
or terminal bonds in polynuclear carbonyls. Examples
➢ Possibility of dimerization or polymerization. Examples
➢ Prediction of the stability of carbonyls for the members of the early
transition series. Examples
➢ Oxidation state change. Examples
➢ Mechanistic paths of ligand substitution reactions in organometallics.
Examples
➢ Polymerization and formation of M—M bonds. Examples

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Counting electrons in complexes

❑ There are two popular procedures for electron counting

❑ They are: neutral atom (NA) method and oxidation state(OS)

method

❑ The neutral atom method does not require correct assignment of

oxidation states

❑ Either of the two methods may be used but they must not be
mixed

❑ Before using any of these methods, one must have a prior idea
about the number of electrons donated by a particular ligand

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Ligand contributions to electron counting

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Counting electrons in complexes with neutral ligands

❑ The electron count for neutral ligands is same for NA or OS

methods.

❑ Verify if the following complexes obey 18-electron rule or not:

• Cr(CO)6
• Ni(PF3)4
• Fe(CO)4PPh3

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Counting electrons in complexes with neutral ligands

❑ Verify if the following complexes obey 18-electron rule or not:

}
• Mn(CO)5
• Co(CO)4 17 e- species
• [Mn(CO)5]-
• [Co(CO)4 ]- } 18 e- species

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Counting electrons in dimeric species

❑ Verify if the following complexes obey 18-electron rule or not:

• Mn2(CO)10
• Co2(CO)8

Hint: each compound has a metal-metal single bond (two-electron) bond

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
e- count in dimeric species vs. molecular structure analysis
❑ In the cobalt dimer, two of the CO ligands are
bridging. This does not affect the electron count. CO
being terminal or bridging always donates 2 e- to the
complex.
❑ In the Co dimer, M—M bond was not a necessity.
However the 18e- rule predicts such a bond, further
supported and confirmed by its diamagnetism and
structural analysis.

Ball and stick

models

Mn2(CO)10 Co2(CO)8
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Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Counting electrons in complexes with ionic ligands

❑ The differences b/w NA and OS methods of electron

counting appears when the metal is in a non-zero OS
and the ligands are ionic.
• [PtCl4]2-
• HMn(CO)5
6e-

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Dependence of e- count on the binding mode

M Cl: + M M Cl M

❑ a halide ligand bound to a metal centre is capable of contributing

an additional nonbonding e- pair to a second metal centre.
NA OS

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Dependence of e- count on the binding mode

NA OS
? ?

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Dependence of e- count on ligands’ hapticity
❑ unsaturated organic ligands, such as allyl (C3H5-), cyclopentadienyl
(C5H5-), benzene, etc. can bind to a metal ion in multiple ways
depending on its hapticity.

❑ The ηx : the number of ligand atoms simultaneously bound to a metal

centre

η5 η3 η1

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Dependence of e- count on ligands’ hapticity

❑ Predict if the following compound follows the 18-electron rule or not.

W(CO)2(C5H5)2

Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.: Inorganic Chemistry:
Principles of Structure and Reactivity; Pearson Education, 2006.
BITS Pilani, K K Birla Goa Campus
Applications of the 18-electron Rule
In general 18-electron rule is remarkably important in understanding the
structure, stability and property of an organometallic compound.
➢ Prediction of the number of metal-metal bonds/ formation of bridging
or terminal bonds in polynuclear carbonyls. Examples
➢ Possibility of dimerization or polymerization. Examples
➢ Prediction of the stability of carbonyls for the members of the early
transition series. Examples
➢ Oxidation state change. Examples
➢ Mechanistic paths of ligand substitution reactions in organometallics.
Examples
➢ Polymerization and formation of M—M bonds. Examples

BITS Pilani, K K Birla Goa Campus

Applications of the 18-electron Rule
Verify if the following compounds follow the 18 e- rule or not:

i. [Fe(CO)2(NO)2]

ii. [Fe(CO)2(η1-Cp)(η5-Cp)]

iii. [Mn(CO)4(η3-C3H5)]

iv. [Fe(CO)3(η4-C4H4)]

v. [Fe(CO)3(η4-C7H8)]

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Applications of the 18-electron Rule
Verify if the following compounds follow the 18 e- rule or not:

vi. [Cr(CO)3(η6-C7H8)]
vii. [Cr(η6-C6H6)2]
viii. [Cr(CO)3(η6-C8H8)]
ix. [Fe(CO)3(η4-C8H8)]
x. [Fe(CO)(η5-C5H5)(η3-C7H7)]
xi. [W(CO)2(η3-C5H5)(η5-C5H5)]

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