CHM102A: General Chemistry

Inorganic Chemistry: Lecture 6A

Sabuj Kundu
sabuj@iitk.ac.in
1
 18-Electron Rule
❑The 18e rule is a way to help us decide whether a given
d-block transition metal organometallic complex is likely
to be stable.

❑CH5 requires a 5-valent carbon and is therefore not

stable. Stable compounds, such as CH4, have the noble gas
octet, and so carbon can be thought of as following an 8e
rule.

❑Carbon using its s and three p orbitals to form four

filled bonding orbitals and four unfilled antibonding
orbitals.
2
 18-ELECTRON RULE

❑The 18e rule, which applies to many low-valent

transition metal complexes, follows a similar line of
reasoning.

❑ The metal now has one s, and three p orbitals, as

before, but now also five d orbitals. We need 18e to fill all
nine orbitals; some come from the metal, the rest from
the ligands.

❑The resulting configuration is analogous to the closed

shell present in the group 18 elements and is therefore
called the noble gas configuration.
3
 Ionic vs Covalent Model
❑There are two conventions for counting electrons: the
ionic and covalent models.

❑Both methods lead to exactly the same net result.

❑They differ only in the way that the electrons are

considered as “coming from” the metal or from the ligands.

❑HMn(CO)5: We can adopt the covalent model and argue

that the H atom, a 1e ligand, is coordinated to a 17e
Mn(CO)5 fragment. OR

❑Consider the complex as being an anionic 2e H− ligand

coordinated to a cationic 16e Mn(CO)5+ fragment.
4
 Ionic Method
❑ The ionic method always assigns filled valences to the ligands.

❑ For example, H group is now considered H-, as well as other groups

such as halide, hydroxyl and methyl groups.

❑ These groups now contribute one more electron than they do in

covalent method and oxidize the metal center when a bond is
formed.

❑ Groups with neutral charge in octet structure, such as CO and NH3,

behaves the same as in valence methods.

5
 Steps for ionic counting method:
❑ Determine the overall charge of the metal complex.

❑ Identify the charges of the ligands, and the numbers of e- they

donate.

❑ 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)

❑ If metal-metal bond is present, one bond counts for one

electron for each metal atom.

❑ Add up the electron count of the metal center and the ligands.
6
Common Ligands and Their Electron Counts

a Linear NO is considered as NO+ on the ionic model

7
 Ligand Ionic Charge
H 2 (H-) -1
Cl, Br, I 2 (X-) -1
OH, OR 2 (OH-,OR-) -1
CN 2 (CN-) -1

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

NO (bent M-N-O) 2 (NO-) -1

NO (linear M-N-O) 2 (NO+) +1
CO, PR3 2 0
NH3, H2O 2 0
=CRR' (carbene) 2 0
H2C=CH2 (ethylene) 2 0
CNR 2 0
=O, =S 4 (O2-, S2-) -2
η3-C3H5 (π-allyl) 2 (C3H5+) +1
≡CR (carbyne) 3 0
≡N 6 (N3-) -3
en (Ethylenediamine) 4 0
bipy (Bipyridine) 4 0
butadiene 4 0
η5-C5H5 (cyclopentadienyl) 6 (C5H5-) -1
η6-C6H6 (benzene) 6 0

η7-C7H7 (cycloheptatrienyl) 6 (C7H7+) +1 8

 Common Ligands and Their Electron Counts

❑The two resonance forms show how we can consider allyl groups
in which all three carbons are bound to the metal as LX ligands.

❑This can also be represented in the delocalized form.

❑In such a case, the hapticity of the ligand, the number of ligand
atoms bound to the metal, is three and so A, referred to as bis-η3-
allyl nickel, or [Ni(η3-C3H5)2].

9
A
 Common Ligands and Their Electron Counts
❑The Greek letter κ (kappa) is normally used instead of η when
describing ligands that bind via heteroatoms, such as κ2-acetate.

❑The electron count of the η3 form of the allyl group is 3e on the

covalent model and 4e on the ionic model.

❑The allyl group can also bind in another way (B). Since only one
carbon is now bound to the metal, this is the η1-allyl form.

❑In this bonding mode, the allyl behaves as an X-type ligand, like a
methyl group, and is therefore a 1e ligand on the covalent model and
a 2e ligand on the ionic model. 10
 hx Hapticity
❑ “eta-x” indicate how many contiguous donor atoms of a p-system
were coordinated to a metal center. Hapticity is used to describe
the bonding mode of a ligand to a metal center.
❑For all-carbon based ligands:
❑x = odd number; indicate anionic ligands (e.g., h5-Cp, h1-allyl or h3-
allyl). The no of electrons donated (ionic method) by the ligand is
equal to x + 1.

❑x= even number; indicate neutral carbon p-system ligands (e.g., h6-
C6H6, h2-CH2=CH2, h4-butadiene). The no of electrons donated by
the ligand equal to x.
Varying Hapticity: Varying Electron Contribution

2 electron donor

4 electron donor

6 electron donor

A molecule can have the same ligand in

different hapticities.

12
Electron counting on the ionic models

13
Electron counting on the ionic models

14
Ionic method Electron Count

15
Ionic method Electron Count
Rh(+1) d8
PR3 2e-
h4-C5H5Me 4e-
h3-C3H5- 4e-
Total: 18e-

Re(+1) d6
2 PR3 4e-
2 CO 4e-
CH3- 2e-
CH2=CH2 2e-
Total: 18e-
16
 Bridging Ligands: Electron Counts
❑Bridging ligands are very common and are prefixed by the symbol μ.

❑On the ionic model, a bridging Cl− donates a pair of electrons to

each of two LnM+ groups.

❑For electron counting purposes, we can consider that that Cl− is a

2e donor to each metal via two lone pairs. 17
 Bridging Ligands: Electron Counts
❑A bridging carbonyl is like a ketone from the point of view of
electron counting; it is a 1e donor to each metal. (This is true for
both models because users of the ionic model regard CO as a neutral
ligand even when bridging.)

❑Other ligands of the same type are bridging methylene, M−CH2−M,

and bridging oxo, M−O−M, which are 2e ligands on the ionic model.

18
 18-electron Rule: Limitations
❑There are many cases in which the electron count for a stable
complex is not 18; examples are
❑MeTiCl3,8e;
❑Me2NbCl3, 10e;
❑WMe6, 12e;
❑Pt(PCy3)2, 14e;
❑[M(H2O)6]2+ (M = V, 15e; Cr, 16e; Mn, 17e; Fe, 18e),
❑CoCp2, 19e;
❑ NiCp2, 20e;
❑For the 18e rule to be useful, we need to be able to predict when it
will be obeyed and when it will not.

❑The rule works best for hydrides and carbonyls because these are
sterically small, high-field ligands. Because they are small, as many
generally bind as are required to achieve 18e.
19
 18-electron Rule: Limitations
❑The rule works least well for high-valent metals with weak-field
ligands. In the hexaaqua ions [M(H2O)6]2+ (M = V, Cr, Mn, Fe, Co, Ni),
the structure is the same whatever the electron count of the metal
and so must be dictated by the fact that six H2O’s fit well around a
metal ion.

❑An important class of complexes follow a 16e, rather than an 18e,

rule because one of the nine orbitals is very high lying and is usually
empty. This can happen for the d8 metals of groups 8–11.

❑Group 8 shows the least and group 11 the highest tendency to

become 16e. When these metals are 16e, they normally adopt the
square planar geometry, but large distortions can occur.

20
Mo(IV): 2
2 h6 Cp: 6X2= 12
Ph: 2
H: 2
Total: 18

Rh(I): 8
h6 Cp: 6
h4 Diene: 4
Total: 18

21
W(II): 4
h6 C6H6: 6
Cl: 2
h3 allyl: 4
PPh3: 2
Total: 18

Fe(II): 6
h5 alkene: 6
3 CO: 6
Total: 18
22
Mo(II): 4
h6 C6H6: 6
h3 alkene: 4
Cl: 2
Bridging Cl: 2
Total: 18

23
24
25