18-electron Rule

In main group chemistry, electron count in molecules are often described by the octet
rule, in which electronic structure can be rationalized on the basis of valence shell
requirements of eight electrons (two s electrons and six p electrons). Similarly, in
organometallic chemistry the electronic structures of many compounds are based on a
total valence electron count of 18 on the central metal atom ((n-1)d10 ns2 np6).
Table. 1. Ligand Contributions to electron counting. NA means Neutral atom
electron counting and OS means Oxidation State Electron Counting.
Terminal Ligands π-Donor Ligands at the Peripheries
Ligand Mode NA OS Ligand Mode NA OS
Carbonyl M-CO 2 2 η1-allyl M C
H2 1 2
Thiocarbonyl M-CS 2 2 η3-allyl M
3 4
Phosphine M-PR3 2 2 η3-enyl M
3 4
1
Amine M-NR3 2 2 η -cyclopentadienyl M
1 2
Dinitrigen M-N N 2 2 η4-cyclopendadienyl M 4 4
H
Dihydrogen M
H
2 2 η5-cyclopendadienyl M
5 6
CH2
Alkene M
CH2 2 2 η6-benzene M
6 6
CH
7
Alkyne* M
CH
2 2 η -cyclopentatrieneyl M
7 6
8
Isocyanide M-CNR 2 2 η -cyclooctatetraenyl M
8 10
M N
Nitrosyl (bent) O
1 2 *sometimes counted as four-electron donor if it
Nitrosyl(linear) M-N O 3 2 is functions as a π-donor
Halogen M-X 1 2
Hydrogen M-H 1 2 Bridging Ligands
Alkyl M-R 1 2 Ligand Mode NA OS
Acyl M-CO-R 1 2 Carbonyl M-CO-M 2 2
Aryl M-Ph 1 2 Halogens M-X-M 3 4
M

Amide M-NR2 1 2 Alkyne C

M
C 4 4
Phosphide M-PR2 1 2 Hydrogen M-H-M 1 2
Alkoxide M-OR 1 2 Alkyl M-(CR3)-M 1 2
Thiolate M-SR 1 2 Amide M-(NR2)-M 3 4
Carbene M=CR2 2 4 Phosphide M-(PR2)-M 3 4
Carbyne M CR 3 6 Alkoxide M-(OR)-M 3 4

1
In neutral atom (NA) electron counting, you don’t need to consider the metal’s
oxidation state and do consider the charge on species. Ligands are considered as neutral.

But in oxidation state (OS) electron counting, you should consider the oxidation state of
the metal and indirectly charge on the species and ligands are taken for accounting.

Neutral Atom Electron Counting Oxidation State Electron Counting

[(η5-C5H5)Fe(CO)2Cl] [(η5-C5H5)Fe(CO)2Cl]
Fe(0) 8 (3d64s2) Fe(II) 6 (3d6 i.e Fe is in +2 oxdn. state)
η5-C5H5 5 (5 electron donor) η5-C5H5 6 (6 electron donor i.e. C5H5−)
2 CO 4 (CO as 2 electron donor) 2 CO 4 (CO as 2 electron donor)
Cl 1 (Cl as 1 electron donor) Cl 2 (Cl as 2 electron donor, i.e. Cl−)
Total 18 Total 18

Some Examples of 18-electron species:

1. (a) NaV(CO)6, (b) Cr(CO)6, (c) Mo(CO)6 (d) HMn(CO)5, (e) Fe(PPh3)(CO)4, (f)
Fe(CO)5, (g) Co2(CO)8, (h) Ni(CO)4, (i) [Mn(CO)5]−, (j) [IrCl(CO)(PPh3)2] (16 e−)

2. Count for M-M Bonding (a) Mn2(CO)10, (b) Co2(CO)8, (c) Tc2(CO)10, (d) Rh2(CO)4Cl2

3. (a) [IrBr2(CH3)(CO)(PPh3)2], (b) W(CO)2(C5H5)2 (find hapticity for C5H5), (C)

[Fe(η5-C5H5)2], (d) [Co(η5-C5H5)2]+, (e) [(η5-C5H5)V(CO)4], (f) [(η5-C5H5)Cr(CO)3]2,
(g) [(η5-C5H5)Mn(CO)3], (h) [(η5-C5H5)Fe(CO)2]2 (i) [(η5-C5H5)Ni(CO)]2

4. (a) [Mo(η6-C6H6)(CO)3], (b) [Cr(η6-C6H6)2], (c) [(CO)5Mn(η1-CH2-CH=CH2)],

(d) [(CO)4Mn(η3-C3H5)]