Organometallic compounds 2

Contents
• Metal Alkyls:
• Important structural features of methyl lithium (tetramer) and trialkyl
aluminium (dimer)
• Concept of multicentre bonding in these compounds
• Role of triethylaluminium in polymerisation of ethene (Ziegler – Natta
Catalyst)
• Species present in ether solution of Grignard reagent and their
structures
• Schlenk equilibrium.
• Ferrocene:
– Preparation
– Structure and aromaticity.
– Comparison of aromaticity and reactivity with that of benzene.
 Organometallic Compounds

• Compounds that contain a Metal-Carbon bond.

• Metal Alkyls, e.g. Tetraethyl lead - Leaded Gas
– Alkyl = methyl, ethyl, tert-butyl, etc.
• Metal = Li, Na, K (alkali metals)
Mg (alkaline earth metals)

Ti Cr Mn Fe Co Ni Cu Zn
Zr Ru Pd Hg
OS Pt
 Metal Alkyls
• General formula R-M (R = alkyl, M = metal)
• The C-M bond is a covalent bond!
• However, C--M+ or R--M+ bond tend to be polarized.
• This is especially true for organometallic compounds
containing the more electropositive metals, i.e. alkali and
alkaline earth metals.
• Generally, the alkyl fragment of the organometallic compound
is very reactive; however this depends on the metal, changing
the metal alters the polarization of the R-M bond.
• Thus different organometallic compounds are used in many
different types of organic reactions.
 Useful Metal Alkyls in Organic Synthesis
C-M
Bond
• Organomagnesium – Mg (C--Mg+)

• Organolithium - Li (C--Li+)

• Organocopper - Cu (C--Cu+)
 Organomagnesium Compounds

Grignard Reagents
• Methylmagnesium chloride - CH3Mg+ Cl-
• Ethylmagnesium bromide - CH3CH2Mg+ Cl-
Draw the structures of:
• Isopropylmagnesium iodide
• Sec-butylmagnesium chloride
Formation of Grignard Reagents:

CH3-Cl Mg, Et2O CH3Mg Cl

 Reactivity of Alkyl Halides

• R-I > R-Br > R-Cl

• Preparation of Grignards from: primary, secondary & tertiary
alkyl halides.
• Grignard formation from aryl halides and allyl halides;
however these may give Wurtz type coupling products.

• I2 maybe used to speed-up the formation Grignard reagents

from alkyl bromides or chlorides
 Organolithium Compounds
Alkyl Lithium Compounds
• Methyllithium – CH3Li
• Ethyllithium - CH3CH2Li

Draw the structures of these Alkyl lithium compounds

• n-propyllithium
• tert-butyllithium

Preparation of organolithium reagents:

2 eq. Li, Et2O

CH3-Br CH3Li + LiBr
 Zieglar-Natta Catalyst

Dr. Ziegler

Dr. Natta

Both earned the Nobel Prize in 1963 !!

 Zieglar-Natta Catalyst
Cl
Cl open Monometallic
Ti *
Cl Cl CH2=CHCH3 Bimetallic mechanism


CHCH3

H2C CHCH3 H2C
CH2  CH2
CH2 CH2
Cl Cl 
Ti Al Ti Al
Cl Ti * + CH2=CHCH3 Cl Ti CHCH3 R R
Cl Cl *
Cl Cl CH2

CH2 CHCH3
HC CH3
CHCH3 H2C
CH2
H2C migration * open H2C CHCH3 CH
Cl CH2 Ti Al Ti Al
Cl Ti * R
Ti CH2CHCH3 Ti CH2 R
Cl
Cl
isotactic syndio

Bimetallic mechanism
- Monometallic Corsee mechanism
 Polyethylene Polymerization
A

B
E

D C
 Zieglar-Natta Catalyst

This image shows the mechanism by which the Ziegler Natta catalyst polymerizes 1-
propene. The image was created by Christine Ann.
 Ferrocene
Fe(ɳ5-C5H5)2: Bis(cyclopentadienyl)
iron(II). It has famous sandwich structure.
 Preparation of Ferrocene
1. By treating iron(II) chloride with grignard reagent
2 (C5H5)-MgBr + FeCl2→ (C5H5)-Fe-( C5H5) + MgBr2 + MgCl2
2. By treating iron halide with sodium cyclopentadienide (inTHF)
C5H6 + Na → C5H5Na + ½ H2
2C5H5Na + FeCl2 → (C5H5)-Fe-( C5H5) + 2NaCl
3. By reaction of iron halide with cyclopentadiene in presence of strong
base
2C5H6 + FeCl2 + 2(C5H5)2NH → Fe (C5H5)2 + 2(C5H5)2NH2Cl
Laboratory preparation
Cracking of dicyclopentadiene
1. Thermometer
2. Condenser
3. Vigreux column
Nitrogen bubbler
4. Heating mantle
Variac
5. Necks round bottom
flask
6. Ice-water
7. If the distillation is
delayed and the
actual preparation of
ferrocene
 Description
The preparation of ferrocene in a teaching laboratory
setting can be accomplished by the use of potassium
hydroxide with cyclopentidiene, to form potassium
cyclopentidiene, which is then reacted with Iron (II)
chloride and the resulting slurry purified by
sublimation.
The final product obtained is then characterized using
FTIR and melting point information.

16
Ferrocene
 Structure of Ferrocene
The staggered configuration is due to crystal packing
forces so that carbon carbon and hydrogen hydrogen
repulsions between the two rings are minimum.

Fe 4KJ / mol
Fe

St aggered Eclip sed

Solid p hase Gas p hase
 Ferrocene: the cyclopentadienyl anion
ligand
Ferrocene contains the
cyclopentadienyl anion ligand, (Cy-)
which contributes five electrons for the
18-electron rule, which is to be
expected from the presence of two
double bonds (4 electrons) and a
negative charge (1 electron).
The anion is stable because it is aromatic,
which requires 4n + 2 electrons in the
π–system. Cy- has 5 electrons in the π–
-
system from the five sp2 hybridized C- Cyclopentadienyl
atoms, plus one from the negative
anion (Cy-)
charge, giving six electrons in the π–
system.
 Ferrocene: the cyclopentadienyl ligand

Ferrocene is a remarkable
molecule. It can be sublimed
without decomposition at
160oC. The 18-electron rule
works for ferrocene as
follows:

Fe(0): d8
2 Cy- 10e

18e
Ferrocene: ‘sandwich compound’
 Valence Bond Theory
Explain diamagnetic character and stable 18 electron
outer electronic configuration of molecule.

Fe (II)
3d 4s 4p

Fe(C5H5)2

six pairs of electrons from two C5H5- rings

d2sp3 hybridisation
 Molecular Orbital Theory
• Group theory can then be employed (cf. Cotton) to determine
how these MOs interact with the orbitals of the valence shell
of the Fe2+ atom to give MOs of the entire molecule with the
correct molecular symmetry, D5d. For example, the interaction
of the dyz orbital of the metal with E1 MOs of the rings is as
pictured.
 Ferrocene is an extremely stable complex, stable in
Air to temperatures of 500oC, because its 18 valence
electrons occupy only bonding and non-bonding
MOs. Twelve of these electrons are contributed to the
structure by the cyclopentadienyl rings and occupy
the lowest six Ferrocene MOs. The six electrons of
the Fe2+ contribute to the Ferrocene metal-like MOs.
The strictly anti-bonding MOs of Ferrocene are not
occupied
 Chemical reactions of ferrocene
Acetylation

COCH3

H3PO4
Fe + (CH3CO)2O Fe + CH3COOH
 Mechanism of Acetylation
• The electrophile first coordinate with metal atom and oxidise it
from iron (II) to iron (III).
• Then it is transferred to C5H5 ring.
• A proton is expelled from C5H5 ring and iron (III) is reduced to
iron (II).
H
E E
E+ - H+
Fe Fe+ E
Fe+ Fe
Reaction with mercuric acetate

HgOAc HgOAc

Fe + Hg(OAc)2 CH3OH
Fe Fe

HgOAc

I2 I2

I I

Fe Fe

M onosubstituted Disubstituted
Friedel Craft’s alkylation
CH2CH3

Fe + C2H4 Anh. AlCl3 Fe

100oC, 230 atm

Mannich condensation
CH2-N(CH3) 2
H

Fe + H-C=O + (CH3)2NH Fe
Sulphonation
SO 3H

Fe + H2SO 4 (CH3CO)2O
Fe

SO 3H

Fe + H2SO 3Cl (CH3CO)2O

Fe

Reaction with alkyl lithium

Li Li
n-BuLi n-BuLi
Fe Fe Fe

Li
 SiM e3

Fe
COOH

Fe
CO 2/H2O
M e3SiCl

Li NO2 NH2

N 2O 4 Fe/HCl
Fe Fe Fe

HgCl
Hy droly sis B(OR)3

Fe
B(OH)2 HgCl 2

Fe Hg(OAc) 2,LiCl
Br2
CuBr2
Br

Ag2O
Fe

Fe Fe