Module III

Organometallic Chemistry

• Organometallic compounds: The compounds formed

between metal and organic compounds containing
metal-carbon bond(s).

• The metal in such a compound is bonded to carbon of an

organic molecule.
 Zeise's salt
Zeise's salt was one of the first organometallic
compounds reported.
W. C. Zeise, University of Copenhagen, prepared this
compound in the 1820s while investigating the
reaction of PtCl4 with boiling ethanol, and proposed
that the resulting compound contained ethylene.

Zeise's proposal was decisively supported in 1868 when Birnbaum prepared the
complex using ethylene.

Zeise's salt received a great deal of attention during the second half of the 19th
century because chemists could not properly explain the molecular structure of the
salt. This question remained unanswered until the advent of x-ray diffraction in the
20th century.

Potassium trichloro(ethene)platinate(II)
η2-ethylene ligand
 Why organometallic chemistry ?
From practical point of view:
1. Useful for chemical synthesis, especially catalytic processes,
e.g. In production of fine chemicals
In production of chemicals in large-scale reactions could not be achieved
traditionally

2. Organometallic chemistry is related to material sciences.

e.g. Organometallic Polymers
Small organometallic compounds:
Precursors to films for coating (MOCVD), Luminescent
materials
PBu3 PBu3
Pt C C C C Pt C C C C
n n
PBu3 PBu3
3. Biological Science. Organometallic chemistry may help us to
understand some enzyme-catalyzed reactions.

e.g. B12 catalyzed reactions.

H R

R
H
From academic point of view:
* Organometallic compounds display many unexpected
behaviors- discover new chemistry- new structures e.g.

H H
H3N: M M M M
M M H SiR3

C C C C
M
M C M C
 Nobel -Prize Winners related to the area:

Victor Grignard and Paul Sabatier (1912): Grignard reagent

K. Ziegler, G. Natta (1963) : Zieglar-Natta catalyst

E. O. Fisher, G. Wilkinson (1973) : Sandwich compounds

K. B. Sharpless, R. Noyori (2001) : Hydrogenation and

oxidation

Yves Chauvin, Robert H. Grubbs, Richard R. Schrock (2005):

Metal-catalyzed alkene metathesis Forum.html Chemistry.html
Organometallic compounds

• These compounds can be seen as having covalent

bonds between the metal and the carbon atoms.
• In general compounds having a metal-ligand bond of
considerable covalent character have similar
chemistry and follow the chemical behavior of
organometallic compounds
• Metal‐cyano complexes are not considered as
organometallic compounds, while metal carbonyl
complexes are.
In general, metals in organometallic compounds include:
main group metals, transition metals, f-block metals
I. Organometallic Basics
A. An Organometallic Complex contains at least one M—C bond
1) Includes ligands: CO, NO, N2, PR3, H2
2) Doesn’t include CN- (classical coordination chemistry ligand)
3) Both  and  bonding between M and C occur

B. History
1) Zeise’s Salt synthesized in 1827 = K[Pt(C2H4)Cl3] • H2O
a) Confirmed to have H2C=CH2 as a ligand in 1868
b) Structure not fully known until 1975

2) Ni(CO)4 synthesized in 1890

3) Grignard Reagents (XMgR) synthesized about 1900

a) Accidentally produced while trying to make other compounds
b) Utility to Organic Synthesis recognized early on
4) Ferrocene synthesized in 1951

a) Modern Organometallic Chemistry

begins with this discovery

b) Many new ligands and reactions

produced ever since

5) Organometallic Chemistry has really been

around for millions of years

a) Naturally occurring Cobalimins

contain Co—C bonds

b) Vitamin B12
 Types of bonds possible from Ligands

Language: All bonds are coordination or coordinative

Remember that all of these bonds are weaker than

normal organic bonds (they are dative bonds)

Simple ligands e.g. CH3-, Cl-, H2 give s (sigma) bonds

 systems are different e.g. CO is a s donor and p

acceptor

Bridging ligands can occur between two metals

Metal-metal bonds occur and are called d bonds –they

are weak and are a result of d-d orbital overlap
II.Ligands and Nomenclature‐ Common Organic Ligands

–Binding Modes
• Bridging is possible with
organometallic ligands
 Ligands

• Those ligands with a single ligating atom are called monodentate ligands, and
those with more than one ligating atoms referred to as polydentate ligands
(chelate ligands).
• Bidentate ligands:
 Ligands

• polydentate (chelate) ligands:

Hapticity (η): Different numbers of atoms of the organometallic
ligand may be involved in bond and is called the “Hapticity” of the
ligand
 Hapticity (η) – Bridging Ligand
• A ligand with carbon-donor atoms with unsaturation can exhibit multiple bonding
modes
• Hapticity gives number of carbon atoms from the ligand that are directly bonded
to the metal, denoted by ‘ηn’, where n is the number of atoms.
For example: Cyclopentadienyl ligand
Allyl ligand

M
η1 η3

• Some ligands can bond to more

than one metal atom in the same
complex. They are referred to as
bridging ligand, denoted as µn,
where n is the no. of metal.
Chelation vs Bridging
 Other common organometallic ligands

M H M C M C
C M M

M CO M CNR M N2
H H
M CS M NO M PR3 M M
H X

M M
M M
M
M

M C

M C
 18 Electron Rule (Sidgwick, 1927)
• Organometallic chemistry gives rise to many “stable”
complexes - how can we tell by a simple method ?
• Every element has a certain number of valence orbitals:
1 { 1s } for H
4 { ns, 3´np } for main group elements
9 { ns, 3´np, 5´(n-1)d } for transition metals

s px py pz

dxy dxz dyz dx2-y2 dz2

 18 – Electron Rule

• Sidgwick (1920s) attempted to account for bonding in transition metal

complexes by extending the octet theory of Lewis.

EAN = Z‐ON + 2 (CN)

• Stability was assumed to be attaining of a noble gas configuration for the metal.

EAN (Effective Atomic Number) = sum of the electrons on the metal plus the
electrons donated by the ligands

• EAN rule is said to be obeyed when EAN equal to 36 (Kr), 54 (Xe) or 86 (Rn).
• Therefore, every element wants to be surrounded by 2/8/18 electrons

– For main-group metals (8-e), this leads to the standard Lewis structure
rules
– For transition metals, we get the 18-electron rule
• Structures which have this preferred count are called electron-precise
• Every orbital wants to be “used", i.e. contribute to binding an electron pair

The strength of the preference for electron-precise structures depends on the

position of the element in the periodic table

• For early transition metals, 18-e is often unattainable for steric reasons -
the required number of ligands would not fit
• For later transition metals, 16-e is often quite stable (square-planar d8
complexes)
• Addition of 2e- from 5th ligand converts complex to 5 Coordinated, 18e- ,
marginally more stable
link
The 18 electron rule – The inorganic chemist’s “octet” rule
Knowing how many valence electrons "belong to" a transition metal
complex allows us to make predictions about the mechanisms of reactions
and the possible modes of reactivity.

Counting Electrons
1) The octet rule governs organic and simple ionic compounds: s + 3p orbital

2) The 18-electron rule governs organometallics (with many exceptions)

a) s + 3p + 5d orbitals
b) Donor ligands provide the electrons other than the d-electrons

There are two distinct methods that are used to count electrons:

1. Donor pair method (Effective atomic number/ ionic method or

oxidation number method)

2. The neutral ligand method (covalent method)

 1. The “neutral‐ ligand” method of electron counting

o Each metal atom and ligand is treated as neutral.

o Count all valence electrons of the metal atom and all the electrons donated
by the ligands
(If the complex is charged, add or subtract the appropriate number of electrons to the
total).
o Ligands are defined as:
o L type if they are neutral two-electron donors - eg CO, PMe3
o X type if, when they are considered to be neutral, one-electron radical donors
(eg. H, CH3).
o mix of both : Hapticity
Electron counting – Neutral atom method

[Fe(CO)5] [HMn(CO)5]

Metal Fe 8 e⁻ Metal Mn 7 e⁻

Ligand 5 × CO 10 e⁻ Ligand 5 × CO 10 e⁻

Charge 0 0 e⁻ Ligand H 1 e⁻

Total 18 e⁻ Charge 0 0 e⁻

Total 18 e⁻

[Mn(CO)5]⁻ [Mn(CO)6]+

Metal Mn 7 e⁻ Metal Mn 7 e⁻
Ligand 5 × CO 10 e⁻ Ligand 6 × CO 12 e⁻
Charge −1 1 e⁻ Charge +1 −1 e⁻

Total 18 e⁻ Total 18 e⁻
2. The “Donor Pair” method of Key point: Ligands are considered to
electron counting donate electrons in pairs (eg.Lewis
base), resulting in the need to treat
a) To determine the total electron some ligands as neutral and others as
count, we must take into account charged.
the charge on each ligand and
determine the formal oxidation
state of the metal.
b) Common organometallic ligands
are assigned an electron count and
charge. 1. The oxidation number of the metal atom is
c) The charge on ligands helps the total charge of the complex minus the
determine d-electron count of charges of any ligands.
metal. 2. The number of d electrons the metal
c) Add up all electrons from Metal d provides is its group number minus its
orbitals and ligands to find total e- oxidation number.
count. 3. The total electron count is the sum of the
d) The donor-pair method requires a number of electrons on the metal atom
calculation of the oxidation and the number of electrons provided by
number. the ligands.
 The “Donor Pair” method of electron counting
• Ligands are considered to donate electrons in pairs (neutral or charged)
• Metal oxidation state considered

o Neutral ligands (eg. CO and phosphine)

two-electron donors
assigned an oxidation number 0.

o Ligands such as halogens, H, and CH3 are formally considered to take

an electron from the metal atom, and are treated as Cl−, H−, and
CH3−
two-electron donors
assigned oxida on number −1

o The cyclopentadienyl ligand, C5H5 (Cp) is treated as C5H5−

six-electron donor
assigned an oxidation number of −1
oxidation number method
Electron counting – Oxidation state method

[Fe(CO)5] [HMn(CO)5]

Metal Fe(0) 8 e⁻ Metal Mn(+1) 6 e⁻

Ligand 5 × CO 10 e⁻ Ligand 5 × CO 10 e⁻
Ligand H− 2 e⁻
Total 18 e⁻
Total 18 e⁻

[Mn(CO)5]⁻ [Mn(CO)6]+

Metal Mn(−1) 8 e⁻ Metal Mn(+1) 6 e⁻

Ligand 5 × CO 10 e⁻ Ligand 6 × CO 12 e⁻

Total 18 e⁻ Total 18 e⁻
 Exercise

• Using both methods, identify the electron count for both complexes?
[IrCl(CO)(PPh3)2] – Vaska’s complex and [Pt(CH2=CH2)Cl3]− – Zeise’s salt
[Pt(CH2=CH2)Cl3]−
[IrCl(CO)(PPh3)2] [IrCl(CO)(PPh3)2] Metal Pt 10 e⁻
Metal Ir 9 e⁻ Metal Ir(+1) 8 e⁻ Ligand CH2=CH2 2 e⁻
Ligand Cl 1 e⁻ Ligand Cl 2 e⁻ Ligand 3 × Cl3 3 e⁻
Ligand CO 2 e⁻ Ligand CO 2 e⁻ Charge −1 1 e⁻
Ligand 2 × PPh3 4 e⁻ Ligand 2 × PPh3 4 e⁻ Total 16 e⁻
Charge 0 0 e⁻ Total 16 e⁻ [Pt(CH2=CH2)Cl3]−
Total 16 e⁻ Metal Pt(+2) 8 e⁻
Ligand CH2=CH2 2 e⁻
• d8 – square planar compounds -16 electrons Ligand 3 × Cl3 6 e⁻

Total 16 e⁻
37
periodic.png
Donor Pair method

Neutral –ligand method

No of metal “d “ electrons = # of valence electron in neutral metal

- metal oxidation state = 8 – 2 = 6

periodic.png
Donor Pair method Neutral –ligand method

periodic.png
periodic.png
Binuclear complex

OC Cl CO
Rh Rh
Cl CO
OC

Neutral atom method Oxidation state method

Metal 2 × Rh 18 e⁻ Metal 2 × Rh(+1) 16 e⁻
Ligand 4 × CO 8 e⁻ Ligand 4 × CO 8 e⁻
Ligand 2 × µ2-Cl 6 e⁻ Ligand 2 × µ2-Cl 8 e⁻
Charge 0 0 e⁻ Total 32 e⁻
Total 32 e⁻
16 per metal
16 per metal

41
Electron‐count preference

[V(CO)6], 17e IrCl(CO)(PPh3)2]

[W(CH3)6] 12e
[Cr(Cp)(CO)2(PPh3)] 17e [Pt(C2H4)Cl3]−

The preference of a metal atom for one

particular geometry and electron count is not
normally so strong that other geometries do
not occur
Metal Carbonyls • Compounds of transition metals with carbon monoxide (CO) as a
ligand.
• Common formula: MX(CO)Y
• Metal carbonyls are known for most of the transition metals

• Most metal carbonyls are toxic!

The decrease in the number of CO ligands from left to right across a period matches the
need for fewer CO ligands to achieve 18 valence electrons.
43
Metal Carbonyls
• Classification of metal carbonyls

One metal, terminal CO

Two metals with M-M bond, bridging CO or both

Simplest of organometallic compounds where M‐C σ bonding is well understood.

CO is one of the strongest π acceptor ligands.

Back bonding (π bonding) and variation in electronic properties of CO can be 44

monitored very efficiently by Infrared spectroscopy
Metal Carbonyls

Fe2(CO)9
Fe(CO)5
Fe3(CO)12

Ni(CO)4

Mo(CO)6
Co4(CO)12

Homoleptic complex is a complex with only one kind of ligand

45
•CO ligands normally take up the most distant locations, like
regions of enhanced electron density in the VSEPR model.

•Eg. Group 6 hexacarbonyls are octahedral; Pentacarbonyliron(0)

is trigonal bipyramidal;

•Tetracarbonylnickel(0) is tetrahedral;
Decacarbonyldimanganese(0) consists of two square-pyramidal
Mn(CO)5 groups joined by a metal–metal bond.

•Coordination number around the metal normally remains six or

lesser.
•Species such as Mn(CO)5, Co(CO)4 dimerize to gain 18 electrons
 Electron counting in Metal carbonyls
[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

Metal Ni(0) 10 e⁻ Metal Fe(0) 8 e⁻ Metal Cr(0) 6 e⁻

Ligand 4 × CO 8 e⁻ Ligand 5 × CO 10 e⁻ Ligand 6 × CO 12 e⁻

Total 18 e⁻ Total 18 e⁻ Total 18 e⁻

[V(CO)6]⁻ [Mn(CO)6]+ [Fe(CO)4]2⁻

Metal V(0) 5 e⁻ Metal V(0) 7 e⁻ Metal Fe(0) 8 e⁻

Ligand 6 × CO 12 e⁻ Ligand 6 × CO 12 e⁻ Ligand 4 × CO 8 e⁻
Charge −1 1 e⁻ Charge +1 −1 e⁻ Charge −2 2 e⁻

Total 18 e⁻ Total 18 e⁻ Total 18 e⁻

3 4 5 6 7 8 9 10
 Complex having metal-
metal-metal bond

• Electron count for [Mn(CO)5] is: 17 e⁻, does not obey 18-electron rule.
• But two such entities form dimeric species with Mn-Mn bond, where each Mn
contributes one electron to the valence shell of the other Mn.

Metal 2 × Mn(0) 14 e⁻
Ligand 5 × CO 20 e⁻
Bond 1 × Mn-Mn 2 e⁻
Total 36 e⁻

18 e⁻ for each metal

48
Is this structure correct?
How to determine the total number of metal‐metal bonds

• Determine the total valence electrons (TVE) in the entire molecule

(that is, the number of valence electrons of the metal plus the Mn2(CO)10
number of electrons from each ligand and the charge); say, it is A

• Subtract this number from n × 18 where n is the number of

metals in the complex, that is, (n × 18)– A; say, it is B

(a) B /2 gives the total number of M–M bonds in the complex

(b) A/n gives the number of electrons per metal.
If the number of electrons is 18, it indicates that there is
no M–M bond;

if it is 17 electrons, it indicates that there is 1 M–M bond;

if it is 16 electrons, it indicates that there are 2 M–M

bonds and so on.
Examples

34/2 = 17; 1

3 4 5 6 7 8 9 10
 Complex having metal-
metal-metal bond - Exception

Metal‐Metal Bond
[V(CO)6] [V2(CO)12]
cannot dimerize
Metal V(0) 5 e⁻
Ligand 6 × CO 12 e⁻

Total 17 e⁻

[V(CO)6] is 17 electrons system but it cannot dimerize to form

[V2(CO)12].

Explanation: Steric crowding around the small sized ‘V’.

[V(CO)6] is stable at low temperature but easily reduced to [V(CO)6]−

52
Use of Electron Counting?
 Exceptions to the 18 Electron Rule
d d d d d d d d d s
21 22 23 24 25 26 27 28 29
ZrCl2(C5H5)2 =?
Sc Ti V Cr Mn Fe Co Ni Cu
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper
TaCl2Me3 =? 39 40 41 42 43 44 45 46 47

WMe6 = ? Y Zr Nb Mo Tc Ru Rh Pd Ag
Yttrium Zirconium Niobium Molybdenum Technetium Ruthenum Rhodium Palladium Silver

Pt(PPh3)3 = ? 57 72 73 74 75 76 77 78 79

IrCl(CO)(PPh3)2 = ? La Hf Ta W Re Os Ir Pt Au
Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold

Early Transition Middle Transition Late Transition

Metals Metals Metals
16e and sub-16e 18e 16e and sub-16e
configurations configurations configurations
are common are common are common
Coordination Coordination Coordination
geometries geometries geometries
higher than 6 of 6 are common of 5 or lower

link
I. ZrCl2(C5H5)2 => Zr (4) + [2 x Cl(1)] + [2 x C5H5(5)] =16

II. TaCl2Me3 => Ta(5) + [2+ x Cl(1)] + [3 x M(1)] =10

III. WMe6 => W(6) + [6 x Me(1)] =12

IV. Pt(PPh3)3 => Pt(10) + [3 x PPh3(2)] =16

V. IrCl(CO)(PPh3)2 => Ir(9) + Cl(1) + CO(2) + [2 x PPh3(2)] =16

• Early transition metals (Zr, Ta, W)

• Several bulky ligands (PPh3)
• Square planar d8 , e.g. Pt(II), Ir(I)
• σ-donor ligands (Me)
[Pt(PCy3)3] – triogonal; 16e
 Bonding in organometallic compounds
 Transition metal organic compounds have different types of bonding
(Sigma, pi, and delta bonding)
9 { ns, 3´np, 5´(n-1)d } for transition metals
These can form sigma, pi and delta bonds

s
px py pz

dxy
dxz dyz dx2-y2 dz2

 Linear combination (LCAO)of these orbitals with the ligand orbitals

results in molecular orbitals
Types of bonds between metals  Hg2Cl2
Metal-Metal bond in poly metallic compound  W2Cl(NMe2)5
 The possibility of quintuple (five) bond
 Two dz2  Two dxz, dyz  Two dxy, dx2y2
 Types of bonds possible from Ligands
1.  (sigma) donor bonds
 All bonds are coordination or coordinative and are weaker than normal
organic bonds
 The donation from s, p, or spn hybrid orbitals of the ligand
 Simple ligands e.g. CH3-, Cl-, H2 give  donor bonds
2. Synergic bonds:- Accepting and donor nature of Bonds
 Ligand donate electron to the metal ( donation)
 At same time metal can donate its d electrons to the same ligand if
empty orbitals with appropriate energy are available (accepting ligands)
e.g.  systems (CR2=CR2, CO, is a  donor and p acceptor

Metal dihydrogen bond

Metal CO bond
Carbon monoxide ligand :C
:C
O
 Good ligand in stabilizing Metal in its low
oxidation state,
 eg: Fe(CO)5, Ni(CO)4

 Could donate lone pair of electron  Accept electrons to the empty ABMO
on Carbon to metal d orbital (* orbital) from metal d orbital

 When no back bonding, M-CO  With back bonding M=C=O

 Weaken the CO triple bond
 Bonding in Metal Carbonyls
“Stable complexes are those with structures such that each atom has only a small
electric charge. Stable M-L bond formation generally reduces the positive charge on
the metal as well as the negative charge and/or e- density on the ligand. The result is
that the actual charge on the metal is not accurately reflected in its formal oxidation
state” – Pauling; The Nature of the Chemical Bond, 3rd Ed.; 1960, pg. 172.

• Resonance structure of a metal carbonyl

• Carbon monoxide is a σ‐donor π‐acceptor ligand

• Dipole moment of CO is very small 0.1D. But, negative dipole is located on ‘C’

63
 18 electron rule for octahedral compounds of d group metal

 18 electrons are stable configuration

for octahedral complexes ML6 type 9 ABMOs

(explained using MO diagram)

Cr(CO)6
 Total Nine bonding (9 BMOs)
interactions are available for metal
 BMOs
 For ML6, Six sigma bonding
interactions are possible,
 When acceptor is present , three 
more bonding (dxy,dxz,dyz) 9 BMOs

Sigma
BMOs
19 e ML6 compounds are good reducing agents
 16 electron stable configuration: for d metal square
planar-SP or tetrahedral-Td ML4 OM compound

For ML4, out of 9 metal orbitals

one became ABMO
 Eight bonding interactions are available
so 16 electrons
 Four sigma bonding and Anti bonding

 When acceptor is present , four more

bonding
 Stable for d8 configuration
 BMOs
Addition of 2e- from 5th ligand converts
complex to 5 Coordinated
18e- , marginally unstable 8 BMOs

• Common for Group 9,10 elements Sigma

• Rh(I), Ir(I), Pd(II), Pt(II) BMOs
 IR spectroscopy of Carbonyl compounds
Gives a clear evidence for back bonding
 For CO gas, bond length is 1.128 A0,
 Wave number of absorption = 2143 cm-1
M‐CO compounds wave number of
absorption reduces to 2100‐1700 cm‐1
 The position of IR absorption depends on the bonding mode of the
CO
1. the amount of electron density on the metal being π-back-
bonded to the CO
2. Symmetry of the compound
3. CO as a Terminal ligand or a bridging
1. Effect of back bonding in the bond length of M:CO
• The C−O bond order (force constant) and the frequency of IR absorption are
directly proportional.

• More the magnitude of back bonding, more the decrease in bond order of CO
ligand as compared to free CO and thereby a decrease in C−O stretching
frequency.

Bonding is somewhere between

M-CO M=C=O
no back-bonding complete back-bonding.
Effect of oxidation state of metal
• Consider a M in iso-electronic in neutral, positively or negatively charged forms

filled vacant
M1 is not a better donor to CO as
M1 +ve compared to M2 because of +ve
M1 C O
charge on M1.

filled vacant

M2 neutral
M2 C O

M3 is a better donor to CO as
compared to M2 because of -ve
filled vacant charge on M3.

M3 -ve
M3 C O Order of metal carbonyl forming ability
M(n+) < M(0) < M(n-)
e. g. Fe(+2) < Fe(0) < Fe(−2)
Ni(0) < Co(−1) < Fe(−2)
2. Effect of mode of attachment of CO ligand(terminal Vs bridging)
• In case of a bridging CO group, there is back donation from at least two metal
centers. Due to this the stretching frequency is lower than a terminal CO ligand.

2000 cm−1 2018, 1826 cm−1 69

1620 cm−1
 The number (and intensity) of the carbonyl bands one observes depends on the
number of CO ligands present and symmetry of the metal complex

IR spectrum of the carbonyl region for Fe(CO)5