Organometallic Chemistry

Introduction

1
 Organometallic Compound
• An area which bridges organic and inorganic chemistry

• A branch of coordination chemistry where the complex has one

or more metal-carbon bonds

• Organometallic compounds (metal organyls, organometallics) are

defined as materials which possess direct, more or less polar
bonds Mδ+— Cδ- between metal and carbon atoms.

C always more electronegative compared to M

2
 Prerequisite

• Historical background
• Oxidation states
• Periodic table (periodic trend)
• Electronic configuration
• d-orbitals
• Back-bonding
• Properties of ligands like alkenes, alkynes, phosphines etc.

3
 Reference Books

• The Organometallic chemistry of the transition metals, R.H.

Crabtree, John Wiley.
• Basic Organometallic Chemistry: Concepts, Syntheses and
Applications, B. D. Gupta and Anil J. Elias, Universities Press &
CRC Press
• Organometallics, Christoph Elschenbroich, Wiley VCH,
Weinheim.
• Organotransition Metal Chemistry. From Bonding to Catalysis.
Edited by John F. Hartwig.

4
Metal--Ligand Interaction
Metal

H3 C C C
H2
C CH2 M π M π*
H3 C
Pb C C
H2C CH
3
H2 C
CH3
donation from π back donation to π*

5
 Orgaometallic Compounds

K2PtCl4 + C2H5OH

K[(C2H4)PtCl3]. H2O + KCl

Discovery 1827

W C Zeise, Danish Structure ~ 150

pharmacist, I789- I847 years later

‘The breakthrough, the isolation of a pure, crystalline compound came when

Also father of the Zeise added potassium chloride to a concentrated PtCl4 /ethyl alcohol
chemistry of reaction solution and evaporated the resulting solution. Beautiful lemon
mercaptans R-SH yellow crystals, often one half inch or more in length were isolated. On longer
exposure to air and light, they gradually became covered with a black crust.
They contained water of hydration, which was lost when they were kept over
concentrated sulfuric acid in vacuo or when heated to around 100°C.
Chemists in those days often reported how the compounds that they had
prepared tasted. Zeise described the taste of this potassium salt as metallic,
astringent and long lasting.’
Dietmar Seyferth, Organometallics, 2001, 20, 2
6
 Orgaometallic Compounds
First σ bonded Organometallic Compound- Diethyl zinc

3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2

Edward Frankland Student of Robert Bunsen (Bunsen

1825-1899 burner fame!). Prepared diethyl zinc while
trying to make ethyl radicals.
Frankland coined
the term
“Organometallic”

As the early 1850s English chemist Edward Frankland described

flasks exploding, throwing bright green flames across his lab, as
he heroically distilled dialkylzinc compounds under an atmosphere
of hydrogen.
7
 Orgaometallic Compounds
Metal carbonyls

The Mond process of Nickel purification

200 °C
NiO + H2 ( from Syn gas) Impure Ni ( Fe and Co) + H2O
excess CO
50 -60 °C

220- 250 °C
Ni(s) + 4 CO Ni(CO)4 (g) bp 42 °C

Ludwig Mond 1839-1909 Ni(CO)4, Fe(CO)5, Co2(CO)8, Mo(CO)6

1890 1891 1910
Father of Metal Carbonyl Chemistry
Founder of Imperial Chemical
‘Mond nickel company’ was making over 3000 tons of nickel
Industry, England in 1910 with a purity level of 99.9%

8
Mo(CO)6
Orgaometallic Compounds
The Grignard Reagent

He was the student of Philippe Barbier (Barbier

reaction [Zn]) He discovered the Grignard reaction
[Mg]) in 1900. He became a professor at the University
of Nancy in 1910 and was awarded the Nobel Prize in
Chemistry in 1912.

9
 Orgaometallic Compounds
Hapto ligands and Sandwich compounds

The hapto symbol, η, with a numerical superscript, provides a

topological description by indicating the number of carbon atoms at a
bonding distance to the metal
Sandwich

Bent Sandwich Half Sandwich Triple decker

& polycyclic

10
 Orgaometallic Compounds
Ferrocene: Fuel additive, smoke suppressant and chiral catalyst precursor

11
 Orgaometallic Compounds
First organometallics in homogeneous catalysis-
The Hydroformylation (1938)

R
C CH2
H
HCo(CO)4 CO,
200 bar, H2
Otto Roelen 110°C
Pioneer in Industrial
homogeneous catalysis R
(1897-1993) CH CH2
First Industrial plant- hydroformylation
H HC
O
O
H
O
O O

O
diethylhexylphthalate [DEHP]
Plasticizer 12
detergents
 Orgaometallic Compounds
Hydrogenation

RHC CH2 + H2 RCH2CH3

Methanol to acetic acid process

CH3OH + CO CH3COOH

Olefin polymerization and oligomerization

* * *
*n *n *n
Isotactic polypropylene Syndiotactic polypropylene Atactic polypropylene

C4-C8 40%
n C10- C18 40 %
C20 & > 20 % 13
Time Line

14
Time Line

15
 Classification
• Classification based on metal
• Main group organometallic Compounds
RMgX, nBuLi, Et4Pb, R3SnX, AlEt3, Et3B etc.

Cacodyl oxide (First Main Group Organometallic Compound)

• Transition Metal organometallic Compounds

Rh(PPh3)3Cl, Pd(PPh3)2Cl2, Et2Zn, R2CuLi etc.

• Lanthanide and Actinide Organometallic Compound

R

Yb

R 16
 Classification
• Classification based on bond present

17
 Types of Ligands
• Most ligands are Lewis bases and thus typically neutral or
anionic, rarely cationic.

• Anionic ligands represented as X and form polar covalent bonds.

• Neutral ligands are denoted as L. Lone-pair donors, π-donors and

σ donors.

18
 Ambidentate Ligands
• Ambidentate ligands are monodentate ligands that have can bind
in two possible places.

19
 Actor and Spectator Ligands
• Actor ligands associate, dissociate or react in some way.
• They are important in catalytic reactions, when they bind to the
metal and engage in reactions that lead to release of a product
molecule.
• Spectator ligands remain unchanged during chemical
transformations but still play an important role by tuning the
properties of the metal.

20
 Multifunctional Ligands
• These are more sophisticated ligands.
• Beyond the simple metal-binding function, they also showed
numerous additional functionalities.
• Sometimes, a complex can be oxidized or reduced, but the
resulting radical is ligand centered so that the metal oxidation
state is unchanged.

21
 Formal Charge and Oxidation State
• Formal Charge (FC): It is the charge assigned to an atom in a
molecule.

22
Formal Charge and Oxidation State

23
 Formal Charge and Oxidation State
• Calculate the oxidation state of the metal ion in the following
complex. R

Yb

24
 Hapticity
• Property of a ligand to coordinate to a metal centre via contiguous
series of atoms.
• Represented by η

Represents the number of donor atoms of a ligand directly attached to

the metal

25
Hapticity

26
 Hapticity

(A) (B) (C)

(D)

(E)

27
 Hapticity

(A) (B) (C) (D)

(E) (F) (G)

28
 Denticity
• Number of donor groups in a single ligand that bind to a central
atom in a coordination complex.
• Represented by k (kappa)

29
18--Electron Rule
18

30
 18--Electron Rule
18

neutral atom oxidation state

method method
CO Ru 8 6 (Ru +2)
PPh3
Ru η3- 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 η5-Cp 10 12
18 18
31
18--Electron Rule
18

32
 18--Electron Rule
18
Ligand Neutral Oxidation state Ligand Neutral Oxidation state
atom atom
Electron Formal Electron Formal
contributi charge contribu charge
on tion
Carbonyl (M–CO) 2 2 0 Halogen ( M–X) 1 2 –1
Phosphine (M–PR3) 2 2 0 Alkyl (M–R) 1 2 –1
Amine (M–NR3 ) 2 2 0 Aryl (M–Ar) 1 2 –1
Amide (M–NR2 ) 1 2 –1 acyl (M–C(O)–R 1 2 –1
Hydrogen (M–H) 1 2 –1 η1-cyclopentadienyl 1 2 –1
Alkene (sidewise) η2- 2 2 0 η1-allyl 1 2 –1
Alkyne (sidewise) η2- 2 2 0 η3-allyl 3 4 –1
η2-C60 2 2 0 η5-cyclopentadienyl 5 6 –1
Nitrosyl bent 1 2 –1 η6-benzene 6 6 0
Nitrosyl linear 3 2 +1 η7-cycloheptatrienyl 7 6 +1
Carbene (M=CR2) 2 4 –2 Carbyne (M≡
≡CR) 3 6 –3
Alkoxide (M–OR) 1 2 –1 Thiolate (M–SR) 1 2 –1
µ-CO (M–(CO)–M) 2 2 0 µ-H 1 2 –1
µ-alkyne 4 4 0 µ-X (M–X–M) 3 4 –1
X = halogen
µ-alkyl 1 2 –1 µ-amido 3 4 –1
(M–(NR2)–M
µ-phosphido 3 4 –1 µ-alkoxide 3 4 –1
33
(M–(PR2)–M (M–(OR)–M
18--Electron Rule
18

34
 18--Electron Rule
18

CO CO CO

CO OC CO
Ni OC Fe Cr
CO OC CO
OC CO
CO
CO CO

O
CO OC CO C CO
OC OC

OC Mn Mn CO OC Co Co CO
OC CO OC CO
CO OC C
O

CO
OC
CO CO
OC CO Ir
OC
CO Os CO OC CO
OC CO Ir Ir
OC CO
Os Os Ir CO
OC CO CO OC
OC CO
CO CO
35
18--Electron Rule
18

36
 18--Electron Rule: Exceptions
18

• The rule is not applicable to organometallic compounds of main

group metals and as well as lanthanides and actinides.
• Sterically demanding bulky ligands force complexes to have less
than 18 electrons.

37
 18--Electron Rule: Exceptions
18
• Some of the octahedral TM complexes do not obey the 18-electron
rule.
• Depending upon the interaction of the metal orbitals with the ligand
orbitals and also upon the nature of the ligand position in
spectrochemical series, the transition metal organometallic
compounds can form into any of the three categories.

• Class-I: Class I complexes for which the number of valence

electrons do not obey the 18 VE rule. number of valence
electrons ≥ or ≤ 18.
• Class-II: Class II complexes for which the number of valence
electrons do not exceed 18. number of valence electrons ≤ 18.
• Class-III: Class III complexes for which the valence electrons
exactly obey the 18 VE rule. number of valence electrons = 18.
38
 18--Electron Rule: Exceptions
18
• Class-I: Number of valence electrons ≥ or ≤ 18.

• the Δo splitting is small and often applies to 3d metals and σ ligands

at lower end of the spectrochemical series. Weak field ligands like F,
Cl-, H2O, NH3.

• In this case the t2g orbital is nonbonding in nature and may be

occupied by 0−6 electrons. The eg* orbital is weakly antibonding
and may be occupied by 0−4 electrons. As a consequence, 12−22
valence electron count may be obtained for this class of compounds.

• For Example: [TiF6]2-12 VE,

[Mn(H2O)6]2+ 17 VE,
[Co(NH3)6]2+ 19 VE,
[Zn(en)3]2+ 22 VE 39
 18--Electron Rule: Exceptions
18
• Class-I: Number of valence electrons ≥ or ≤ 18.

• 12 electrons from the ligands fill the lowest energy orbitals (blue).
Up to 6 metal electrons reside in the t2g set (nonbonding) without
any destabilization of bonding.
• Δo is so small that up to 4 electrons can be put into the eg set.
40
 18--Electron Rule: Exceptions
18
• Class-II: Number of valence electrons ≤ 18.
• In class II complexes, the Δo splitting is relatively large and is
applicable to 4d and 5d transition metals having high oxidation state
and for σ ligands in the intermediate and upper range of the
spectrochemical series.
• In this case, the t2g orbital is essentially nonbonding in nature and
can be filled by 0−6 electrons. The eg* orbital is strongly anti-
bonding and is not occupied at all.
• Consequently, the valence shell electron count of these type of
complexes would thus be 18 electrons or less.
[WCl6] 12 VE
[WCl6]2- 14 VE
[W(CN)8]3- 17 VE
[PtF6]2- 18 VE
41
 18--Electron Rule: Exceptions
18
• Class-II: Number of valence electrons ≤ 18.

• 12 electrons from the ligands fill the lowest energy orbitals (blue).
Up to 6 metal electrons reside in the t2g set (nonbonding) without
any destabilization of bonding.
• Δo is so large that electrons cannot put into the eg set. 42
 18--Electron Rule: Exceptions
18
• Class-III: Number of valence electrons = 18.
• In class III complexes, the Δo splitting is the largest and is applicable
to good σ donor and π acceptor ligands like CO, PF3, olefins and
arenes located at the upper end of the spectrochemical series.

• The t2g orbital becomes bonding owing to interactions with ligand

orbitals and should be occupied by 6 electrons. The eg* orbital is
strongly anti-bonding and therefore remains unoccupied.

[MnH(CO)5] 18 VE
[Co(NO)(CO)3] 18 VE
[Ni(CO)4] 18 VE

43
 18--Electron Rule: Exceptions
18
• Class-II: Number of valence electrons = 18.

9 low energy bonding

MO’s and 9 strongly anti-
bonding MO’s

• 12 electrons from the ligands and 6 metal electrons in the t2g orbitals
fill the lowest energy orbitals (blue). Removal of the d-electron t2g
set would destabilize the bonding.
• Δo is so large that electrons cannot put into the eg set.
44
 18--Electron Rule: Exceptions
18
• Square planar organometallic complexes of the late transition
metals (16e).

Large ∆E

• d8-metals with 4 ligands: 16-electron complexes.

• Common for metals and ligands high in the spectrochemical series.
• RhI, IrI, PdII, PtII, AuIII almost always square planar. NiII can be
square planar, but only with strong pi-acceptor ligands (because 1st
row TMs are lower in spectrochemical series than 2nd and 3rd row
TMs.) 45
 18--Electron Rule: Exceptions
18
• Linear organometallic complexes, d10 metals with two ligands: 14
electron complexes.
• Common for AgI, AuI and HgII.
• For d10 complexes, there is a relatively small energy
difference between the d, s, and p orbitals. This permits
extensive hybridization between dz2, s and pz orbitals

46
 18--Electron Rule: Exceptions
18
• Strong oxidants and reductants: Many 18 electron complexes can be
reduced or oxidized to give 17 or 19 electron complexes.
• Such compounds are often good oxidizing or reducing agents.

47