18e

Rule
ronic structures of many organometallic compounds are based on a tota
e electron count of 18 on the central metal atom. Sidgwick coined the te
gas rule for indication of stability of 18e compounds.
Electron Counting Methods
1) Neutral Ligand / Covalent Method: All ligands are treated as
neutral and are
categorized according to how many electrons they are considered to
donate.
2) Donor Pair/ Ionic Method: Ligands are considered to donate
electrons in pairs, resulting
the need
to[MX
treatLsome
ligands as
c+
ElectroninCounts
for
a b]
neutral and others as charged.
L: A neutral ligand, which can be a lone-pair donor, such as CO or
NH3, a -bond
donor, such as C2H4,or a -bond donor such as H2, which are all 2e
ligands on both
models.
X: Ligands such as H, Cl, or Me, which are 1e X ligands on the

18e
Rule
N: Number of electrons in neutral M
atom.
a and b are the numbers of ligands.
c is the net ionic charge.

Covalent
Model
Number of electrons on metal = N
Number of electrons in ligands = a + 2b
Total electron count = (N) + (a + 2b) c

Ionic
Model
Oxidation state of metal ion = (c + a)
Number of electrons on metal = N a c
Number of electrons in ligands = 2a + 2b
Total electron count = (N a c) + (2a + 2b)
= N + a + 2b c
2

Electron Counts for

Typical Ligands
Covalen Ionic Ligand
t

Covale
nt

Ionic

CO, PR3

H2

H2O,
NH3

N2

R (alkyl,
aryl)

2 or 4

2 or 4

Ligand

H2C CH2

Cl
R

In the covalent method, the linear NO is a 3e donor due to

one and one bond, whereas bent NO is a 1e donor due to
one single covalent bond.
3

Ligand
H2C CH2 2

Electron Counts for Donor Ligands

Covalen Ionic
Ligand Covalen Ionic
t
t
6

2
2
6
6
3

Structures of Metal
Carbonyls
Bonding Modes

Bonding Scheme

-bonding
dx2-y2

-bonding
dxy

Structures of Metal
Carbonyls
Bridging Modes of CO

Structures of Metal
Carbonyls
Both donation (which donates electron density from a bonding
orbital on CO)
and acceptance (which places electron density in C-O antibonding
orbitals) would be expected to weaken the C-O bond and to
decrease the energy necessary to stretch that bond.

The more negative the charge on the organometallic species, the

greater the tendency of the metal to donate electrons to the *
orbitals of CO and the lower the energy of the C-O stretching
vibrations.
Order of C-O bond length: Ti(CO)62- > V(CO)6- > Cr(CO)6 > Mn(CO)6+
> Fe(CO)62+
7

Structures of Simple Metal

Carbonyls

The carbonyls of the Period 4

elements of
Groups 6 to 10 obey the 18-electron
rule;
they have alternately one and two
metal
atoms and a decreasing number of
CO ligands.
10