CHAPTER 2
The 18 valence electron rule
The elementary basis for discussing structure and bonding in organometallic compounds
is based on the 18 valence electron rule and the concept of backbonding or extent of
acceptor capabilities of ligands
Hapticity and sandwich compounds
A number of unsaturated organic ions and molecules such as ethylene, allyl,
cyclopentadienyl and benzene can bind to a metal in more than one way, the different
modes being distinguished by the number of carbon atoms participating in linkage (to be
more precise, one has to see how many carbon atoms are there which are at a bonding
distance from the metal atom). The hapto symbol with a numerical superscript provide
a topological description by indicating the connectivity between the ligand and the central
atom. for e.g. if all the five carbon atoms of a cyclopentadienyl moiety are equidistant
from a metal atom, we term it as 5- cyclopentadienyl.
18 electron rule
This was first proposed by N.V. Sigwick in 1927 who extended the octet theory of G.N.
Lewis and using it to explain coordination compounds. Ligands were considered Lewis
bases and the metal ion in turn acted as a Lewis acid. The rule states that
thermodynamically stable transition metal organometallic compounds are formed when
the sum of the metal d electrons and the electrons conventionally considered as being
supplied by the surrounding ligands equals 18. The sum of the electrons on the metal
plus the electrons donated from the ligands is also called the effective atomic Number,
EAN and when it was equal to 36(Kr), 54(Xe) or 86(Rn), the molecule is found to be
stable as it will have a rare gas configuration. An alternate and general statement is that
when the metal in question achieves an outer shell configuration of ns2 (n -1)d10 np6, there
will be 18 electrons in the valence orbitals and a closed, stable configuration. This rule of
thumb is obeyed with a rather high frequency by organometallic compounds. In general,
the conditions favouring adherence to the 18 electron rule are an electron rich central
metal (one that is in a low oxidation state) and ligands that are good acceptors.
By counting the number of outer shell electrons surrounding each metal atom in a
complex, it is possible to predict whether the complex will be stable as well as in some
cases whether there will be metal-metal bonds present or not. There are two methods of
electron counting namely the neutral atom counting method and the oxidation state
counting method. The neutral atom method is more foolproof as it does not require
correct assignment of oxidation states which is sometimes difficult in organometallic
compounds. However oxidation count method is followed when one has to follow the
changes in the oxidation state of the metal centre in areaction. The following table gives
1
electron contributions for a variety of ligands according to the neutral atom counting
method. Comparison of both the methods are also given below.
Carbonyl (M -CO) 2 halogen( M -X) 1
Phosphine (M - PR3) 2 alkyl (M -R) 1
Amine (M -NR3 ) 2 Aryl (M-Ar) 1
Amide (M –NR2 ) 1 acyl (M-C(O)-R 1
Dihydrogen (side wise) 2 1- cyclopentadienyl 1
Alkene ( sidewise) 2- 2 3- allyl 3
Alkyne ( sidewise) 2- 2 5- cyclopentadienyl 5
2- C60 2 6- benzene 6
Nitrosyl bent 1 7- cycloheptatrienyl 7
Nitrosyl linear 3 hydrogen (M-H) 1
Carbene (M=CR2) 2 Carbyne (MCR) 3
Alkoxide (M-OR) 1 Thiolate (M-SR) 1
- CO (M-(CO)-M) 2 -H 1
-alkyne 4 -X (M-X-M) X= halogen 3
-alkyl 1 - amido (M-(NR2)-M 3
- phosphido (M-(PR2)-M 3 - alkoxide (M-(OR)-M 3
neutral atom oxidation state
method method
Co Ru 8 6 (Ru +2)
PPh3
Ru 3- allyl 3 4
2 PPh3 4 4
PPh3
CO 2 2
charge -1 not required
16 16
Me
N Fe 8 6 (Fe +2)
Me
Fe 2 5-Cp 10 12
18 18
2
How to count electrons and also find number of metal -metal bonds by the neutral
atom counting method.
Fe(CO)4PPh3 Fe 8e Mn(CO)5- Mn 7e
4 CO 8 e 5 CO 10 e
PPh3 2 e Charge 1 e
Total 18 e 18 e
Mn2(CO)10 2Mn 14 e (CH3)3Ta(Cl)2 Ta 5e
10 CO: 20 e 3 Me 3e
1 M-M bond 2e 2Cl 2e
Total 36/2 = 18 e 10 e
O 2 Mo: 12 e Fe3(CO)12 3 Fe : 24 e
CO
C 2 5 Cp: 10 e 12 Co: 24 e
Mo Mo
4 CO: 8 e 3 M-M Bonds: 6
3 M-M bonds: 6 e
C C
O O
Total 36 / 2 = 18 e 54/ 3 = 18 e
It may be noted that for main group organometallics and organometallic compounds of
the f-block elements the 18 electron rule will not be applicable. Among transition metal
organometallics also one finds many exceptions to the 18 electron rule. The 18 electron
rules forms one of the fundamental basis on which many physical and chemical
properties of oragno-transition metal compounds can be explained. The following set of
exercises will help to understand its concept and applicability.
The 18- electron rule can be used to predict the number of ligands a particular metal can
coordinate and the stability/reactivity of a complex. The rule works best for low-valent
metals with small ligands that are strong donors and /or acceptors. Such ligands are
small enough to allow the metal to be coordinatively saturated and give large value of
ligand field splitting and there is a strong preference to fill the d orbitals which will
require 18 electrons. It may be noted that just like the octet rule there are many
exceptions to the 18 electron rule. Some of the common exceptions are
1 Metals with d8 electrons: The d8 metals have a tendency to form square planar 16
electron complexes. This tendency is weak for group 8 (Fe, Ru and Os in zero
oxidation state) and strong for group 9, 10 and 11 [e.g. Rh(I), Pd(II), Pt(II),
Au(III)]. It is well known that square planar 16 electron complexes of d 8 metals
results in completely filled orbitals except the high energy orbital dx2-y2.
1. metals with d0 electrons: Many high valent d0 complexes have lower electron
count than 18. Also sterically demanding bulky ligands also force complexes to
have lower than 18 electrons.
3
Exercises
1. Suggest and draw possible 18 electron structure which can be formed from the
following combination of metal and ligands. Use at least one unit of each ligand
listed for the particular metal. Propose only neutral complexes. Don’t use more
than two metal centres and show your electron counting. If there is more than one
possibility, indicate which will be the stablest. (note that ligands are indicated
without charges)
a) Ru, CO, CH3, PMe3 b) Mo, allyl, Cp, NO
c) Re, Cl, -dppm (Ph2PCH2PPh2) d) Ir, Cp, H, PMe3
2. Consider 18 electron rule as a guide and determine the value of n in the following
complexes
i) Na2Fe(CO)n ii) MnBr(CO)n
iii) W(6-C6H6)(CO)n iv) Rh(5-C5H5)(CO)n
(v) Cr(3-C5H5)(CO)n(CH3) (vi) IrBr2(CO)(PPh3)2(CH3)
3. Predict M if M is a first row transition element and if [M(3-C5H5)(CO)5] is a
stable compound
4. The complex [M(6-C6H6)(CO)2]2 obeys 18 electron rule and has one metal-
metal double bond. Predict M and sketch the probable structure of the complex.
5. A metal complex having as one ligand a substituted cyclopentadienyl group has
the empirical formula FeC9H7O3Cl. The compound is poorly soluble in
hydrocarbon solvents. Assuming that it obeys 18 electron rule, suggest its
structure.
6. Determine the number of metal- metal bonds in the following complexes which
obeys 18 electron rule.
i) (CO)2Rh(-Cl)2Rh(CO)2 ii) (5-C5H5)(CO)Fe((-CO)2Fe(CO)( (5-C5H5)
7. Determine the unknown quantity
a) [CpW(CO)x]2 [has W-W single bond]
b) [(CO)3Ni-Co(CO)3]z
c) [CpMn(CO)x]2 (has Mn = Mn double bond]
d) [(Cp)3Ni3(μ3-CO)2]z
4
e) [CpM(CO)3]2 (has a single M-M bond; M = Ist row TM]
8. The given complexes are thermodynamically stable. Draw the structures and
determine the geometry around the nitrogen atom in both cases. Which among
them is expected to have a shorter metal- nitrogen bond ? Give reasons.
(a) (3- allyl)Ru(CO)2(NO) (b) (5- Cp) Ru(CO)2(NO)
9. The given dimeric rhodium complexes have both symmetrically bridging groups
(H and Cl). The geometry around the rhodium in both cases is square planar.
Draw the possible structures and determine the expected bond order of the
rhodium- rhodium bond in both cases
(a) [(2- ethylene)2Rh(-H)]2 (b) [(2- ethylene)2Rh(-Cl)]2
10 The metal cluster [Ru3(CO)10(PPh3)2] is very stable. Which among the
following will be the actual structure of the molecule. Justify your answer.
OC Ph3P CO OC CO
OC CO OC CO
Ru CO
OC Ru Ru Ru CO Ph3P
CO
OC OC Ru Ru
OC PPh3 CO CO OC CO
A OC PPh3
Ph3P B
O O
C C
OC CO
OC Ru Ru Ru CO
OC C C CO
O O
Ph3P
C