……………Cont’d mode of bonding

In general, the binding modes of the carbon-derived ligands depend upon the

hybridization state of the metal bound carbon atom.

These ligands can thus bind to a metal in many different ways as depicted below.

These ligands can either be of

(a) purely σ−donor type, or

Depending upon the capability of the ligand to form the multiple bonds may also be of

(b) a σ−donor/π−acceptor type, in which the σ−interaction is supplemented by a

varying degree of π−interaction.

Hapto (η) Number (Hapticity)
Hapticity of a ligand, ηn, is the number of atoms of the ligand that are
directly bonded to the metal centre.
Τhe prefix ηn for π−ligands means: the number of carbons (n) bound to the
metal centre
Eg. if all the five carbon atoms of a cyclopentadienyl moiety are
equidistant from a metal atom, we term it as η5‐cyclopentadienyl
ηn Mono, di, tri, tetra, penta hapto… ; where n=1,2,3,4,5…
Electron Counting in Organometallic Chemistry
It is the key in understanding organometallic chemistry
When the metal achieves an outershell configuration of ns 2(n-1)d10np6, there
will be 18e-s in the valence orbital & a closed, stable configuration.
This rule referred to as the 18 e- rule.
The 18-electron rule or EAN Rule
states that thermodynamically stable TMOM cpds are formed when the
sum of d-e-s, donated ligand e-s & charge on complex = 18.
 helpful in predicting the stabilities of organometallic compounds.

 There are two common methods for determining the number of

electrons in an organometallic compound.
Counting of electrons in Organometallic cpds

Neutral atom method Ox.state method

M is taken as in zero ox. state 1st arrive at the ox. state of the M by
for counting purpose considering the number of anionic Ls
present & overall charge of the complex
 (Neutral atom )
(Ox.state)

M-M single bond counts as one electron per metal

Methods of counting: Neutral atom method & Oxidation state method

Complexes in which the fullerene

itself behaves as a ligand
Fe(CO)4(2-C60), Mo(5-C5H5)2(2-C60)

Suggestion: Focus on one counting method till you are confident!!!

Buckminsterfullerene C60 (left) and carbon nanotubes (right) are two
examples of structures in the fullerene family.
Examples of Electron Counting
 • Cr(CO)6
– Total charge on ligands = 0, so charge on Cr = 0, so Cr = d6
– 6 CO ligands x 2 electrons each = 12 electrons
– Total of 18 electrons

• (ή5-C5H5)Fe(CO)2Cl
– Total charge on ligands = 2-, so Fe2+ = d6
– (ή5-C5H5- = 6) + (2CO x 2 = 4) + (Cl- = 2) = 12 electrons
– Total of 18 electrons

• Charged complex: [Mn(CO)6]+

– Total ligand charge = 0, so Mn+ = d6
– 12 electrons from 6 CO ligands gives a total of 18 electrons

• M—M Bond: (CO)5Mn—Mn(CO)5

– Each bond between metals counts 1 electron per metal: Mn—Mn = 1 e-
– Total ligand charge = 0, so Mn0 = d7
– 5 CO ligands per metal = 10 electrons for a total of 18 electrons per Mn
What is the electron count for Fe(CO)4(2-C60), Mo(5-C5H5)2(2-C60)?
Significant of 18-e- rule
i.Explain the stability & existence of the complex
Mn(CO)5, V(CO)6-------17e-…..unstable

[Mn2(CO)10]…..36/2=18e-….the dimer is very stable & well known

ii. The existence of M-M bond is predicted by 18-e rule.
Co2(CO)8 2Co = 2x9=18
8CO=2x8=16
Co-Co= 2---------36 e-
iii. Rationalization of hapticity & bonding characteristics of the complex
W(C5H5)2(CO)2 ……..20 e-s

W(ή5-C5H5) ((ή3-C5H5) (CO)2 -------6+5+3+4=18e-s

Exceptions to the 18e- Rule
There are quite a few examples of organometallics which have 16 VE.
i. Electronic effects
Late TM with d8 electron configurations. e.g. Rh(I), Ir(I), Pd(II), Pt(II)
have a strong tendency to form square planar 16 VE complexes. Similarly, d10
complexes tend to form trigonal 16 VE complexes.

[PtCl3(C2H4)]-… Pt= d8 s2=10 3Cl= 1X3=3; C2H4=2X1=2 ……16e-

The stability of 16 electron complexes, especially with σ-donor π-
acceptor ligands, can be understood by examining a MO diagram.

The electron pairs from the

4 ligands used in σ bonding
occupy the bonding
orbitals.
The dxy, dxz, dyz and dz2
orbitals are either weakly
bonding, non-bonding, or
weakly antibonding.
The dx2-y2 orbital is anti-
bonding, & if filled, will
weaken the σ bonds with the
ligands .
As a result, 16 electrons will produce a stable complex.
 (ii) Steric Effects
Early TM have fewer d-e-s to start with than the middle & late TM, so they must achieve
their 18e count by coordination of a larger number of ligands. If the ligands involved are too
bulky, then low-electron count complexes are formed.

OM complex with more than 18 electrons are also known

Eg.
Generally
Square planar organometallic complexes of the late transition metals (16e).
eg. Pt(PPh3)3 …..Pt(10) + [3 x PPh3(2)] =16
IrCl(CO)(PPh3)2…. Ir(9) + Cl(1) + CO(2) + [2 x PPh3(2)] =16

 Some organometallic complexes of the early transition metals <18 e-s.

e.g.Cp2TiCl2(16), WMe6(12),Me2NbCl3(10),ZrCl2(C5H5)2(16),TaCl2Me3(10)

Sterically demanding bulky ligands force complexes to have <18 electrons.

eg, complexes having PPh3 & the like ligands. Cp2TiC2H4)(16)
 How to determine the total number of M-M bonds?

Determine the total valence electrons (TVE) in the entire molecule (i.e, the # of
VES of the M plus the # of electrons from each L & the charge); say, it is A.
Subtract A from n×18 ; where n is the number of metals in the complex,
i.e., (n×18) –A; say, it is B.
(a) B/2 = the total # of M–M bonds in the complex.
(b) A/n = the # of electrons per metal.
 If the # of electrons is 18, it indicates that there is no M–M bond;
if the # of electrons is 17, it indicates that there is 1 M–M bond & so on

# of electrons # of M-M bond

18 no
17 1
16 2
15 3
17
General properties of OM Cpds
The physical & chemical properties of organometallic compounds vary greatly.
The properties of the organometallic compounds depend in large measure on
the type of carbon-metal bonds involved

 Most are solids, particularly those whose HC groups are ring-shaped or

aromatic

 some are liquids & some are gases.

 Their heat & oxidation stability vary widely.

 Some are very stable, but a number of compounds of electropositive elements

such as lithium, sodium & aluminum  are spontaneously flammable.

 Many organometallic compounds are highly toxic, especially those that are

volatile.
Reactions of Organometallic Complexes with Electrophiles

1. Electrophilic Addition:
Zero-electron reagents (e.g. H+, Me+, CPh3+, AlR3, BR3, HgX2, Cu+, Ag+, CO2,

SO2 etc.) can attack at the

(a) metal (even in 18 e-cpds),
(b) M-L bond, or
(c) ligands.
Many different mechanistic pathways are available for all of these reaction types.
(a) Overall electrophilic addition to the metal
 Oxidative addition by SN2 or Ionic mechanisms involves electrophilic attack on
the metal as the first step (see below):
SN1
Concerted
rxn

SN2

stepwise
rxn
If the 2nd step doesn’t take place, this process is called electrophilic addition rather
than oxidative addition:

Electrophilic addition of other zero-electron donor ligands (e.g. AlR3 or BR3) at

the metal can also occur. However, the formation of stable complexes such as
that shown below is extremely rare.
(b) Overall electrophilic addition to a ligand (ligand remains attached to the
metal)
 Protonations are the most commonly observed example of this reaction
type. Examples are shown below:
Protonation of a metal-hydride to give a dihydrogen complex:

Protonation of an alkene complex. For the example shown below, initial

protonation occurs at the ligand & at the metal (2 competing pathways).
Direct electrophilic attack by D+ on a cyclopentadienyl ring → exo attack (on
the least hindered face).

Electrophilic attack at a coordinated Cp- ring by Hg(OAc)+ or COMe+:

Electrophilic attack {by soft Hg(OAc)2} on a cyclopentadienyl ring → initial attack
at the metal.
Electrophilic attack {by hard “COMe+”} on a cyclopentadienyl ring → initial attack
at the ligand (the acetyl cation attacks both the C5D5- and the C5H5- rings, but
only attack on the former is shown).

2. Electrophilic abstraction (mostly of alkyl groups)

Can occur by a wide variety of different mechanisms:
 Other electrophilic abstraction reactions

Conjugated substituents such as allyl groups can be removed by electrophilic

attack at positions further away from the metal:

Strong electrophiles can also abstract a substituent from the β-carbon:

Strong electrophiles can also abstract a substituent from the α-carbon:
End of Session 2