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Organometallic Chemistry

Book · October 2002

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Fatma S.M. Hassan
Professor of
Inorganic Chemistry
Aswan University
Faculty of Science
Aswan
 CONTENTS
Part 1
-General Survey
-General Comments
-Synthetic Methods
-Chemical Character and Synthetic uses of Organometallics
Compounds
Part 2
-Nontransition Metals
-Mercuration
Part 3
-Transition Metals
-The 18-electron Rule
-The Effective Atomic Number
-Molecular and Electronic Structure of Carbonyls (The EAN
Rule) -Two-electron Ligands
-A description of the bonding of 2-electron ligand to transition
-General comments on 2-electron ligands metals
-Metal Carbonyls
-Preparation of Metal Carbonyls
-Bonding in linear M-C-O-group
-Bonding mechanism
- vibrational spectra of metal carbonyls
-Reactions of metal carbonyls
- Carbonyl Hydrides
 CONTENTS

- Carbonyl halides and Related Compounds

- Carbon monoxide Analogs

- Isocyanide Complexes

- Dinitrogen Complexes

- Donor Complexes of Group V and VI ligands

- Nitric Oxide Complexes

- Linear, Terminal MNO Groups

- Bent, Terminal MNO Groups

- Bridging NO Groups

- Three-Electron ligands

- Bonding in Allyl metal Compounds

- Five-electron ligands

- Bonding in ( ἠ5-C5H5) metal Compounds

- One-electron ligands

- Classification of 1-electron ligands

- General preparative methods

- General Chemical Properties

3
 - The Role of Organotransition Metal complexes in Some
Catalytic reactions

Applications of Organometallic Compounds As Catalysts

(Homogeneous and Heterogeneous Catalysts) :

Hydroformylation

Acetyl formation
Monsanto process

Wacker process

Hydrogenation

Wilkinson's catalyst

Coordination (Ziegler-Natta) Polymerization

- Carbonylation Reactions

- Dinitrogen, Dioxygen and Carbene Transition Metal Complexes

- Dinitrogen Complexes

- Dioxygen Complexes

4
Part 4

Fullerene chemistry

- References

5
6
 ORGANOMETALLIC COMPOUNDS
General Survey:
Organometallic compounds are those in which the carbon
atoms of organic groups are bound to metal atom,

For example,
( OC3H7 = pentyl alkoxide)
An alkoxide such as (C3H70)4Ti is not considered to be an
organometallic compound because the organic group is bound
to Ti by oxygen, whereas C6H5 Ti (OC3 H7)3 is, because a metal
to carbon bond is present.

The term organometallic is usually rather loosely defined

and compounds of elements such as boron, phosphorus, and
silicon which are scarcely, if at all metallic, are included in the
category. eg.

Cl PPh2
(TMS)
Pt CH2
Cl PPh2
7
 Carbon in not, however, restricted to forming bonds with
electronegative elements and many compounds are known in
which carbon groups are covalently bonded to metals (metals
are less electronegative than carbon). These are called
Organomelallic compounds and, until recently, relatively little
was known about their chemistry.
As a results of the low electronegativity of metals,
carbon-metal bonds are polarized so that carbon is now the
negative pole and we have bonds of type.

In addition, metals tend to form positive ions rather than

negative ions and therefore these bonds to carbon break with the
electron pair remaining on carbon.

In reactions between organometallic compounds

and compounds with electronegative substituent, attractive
interaction between two carbon atoms is thus possible and
reactions of this type lead to many useful and important carbon-
carbon bond syntheses.
e.g. Ethyl Li reacts with allyl bromide to give pent-1-ene
CH3CH2 Li +CH2 =CHCH2Br →

8
 It is important to remember that in non-metallic organic
compounds, carbon may not be the only element at the positive
end of a bond dipole. Thus, in alcohols, for example, the
hydrogen atom also bears a positive charge as it does in primary
amines:

These hydrogen atoms are acidic in character (active).

With compounds like this, organometallic compounds usually
react to form a C-H bond as it is easier to break an oxygen -
hydrogen or nitrogen-hydrogen bond than an oxygen-carbon or
nitrogen-carbon bond.

Thus ethyl-lithium reacts with ethanol to form ethane and

lithium ethoxide, rather than butane and lithium hydroxide:

CH3-CH2-Li + CH3CH3 + LiOCH2CH3

Ethane Lithium ethoxide
Not

CH3 CH2-Li CH3CH2

+ LiOH
CH3CH2-O-H CH3CH2 Butane

9
This reaction emphasizes that compounds like ethyl lithium are
very strong bases and will remove protons from very weak
acids.
General Comments:
A few general comments on the various types of compound can
be made first.
1- Ionic compounds of electropositive metals:
The Organo compounds of highly electropositive metals are
usually ionic, insoluble in hydrocarbon solvents and are very
reactive towards air, water, and the like. The stability and
reactivity of ionic compounds are determined in part by the
stability of the carbonation.
Compounds containing unstable anions (e.g. CnH2n+1) are
generally highly reactive and often unstable and difficult to
isolate.
Metal salts of carbanions whose stability is enhanced by
derealization of electron density are more stable although still
quite reactive, examples are (C6H5)3 C- Na+ and (C5H5)2 Ca2+.
2- δ-Bonded compounds
Organo compounds in which the organic residue is bound to a
metal atom by a normal 2-electron covalent bond are formed by
most metals of lower electropsitivity and, of course, by
nonmetallic elements.
In most of these compounds, the bonding is predominantly
covalent and the chemistry is organic-like, though there are

10
many differences from carbon chemistry due to the following
factors.
(a) The possibility of using higher d orbital in for
example:
SiR4 which is not feasible in CR4
(b) Donor ability of alkyls or aryls with lone pairs as in
PEt3, SMe3, etc..
(c) Lewis acidity due to incomplete valence shells as in
BR3 or coordinative unsaturation as in ZnR2.
(d) Effects of electronegativity differences between M-C
and C-C bonds.
Transition metals may form simple alkyls or aryls but
these are normally less stable than those of main group elements
(will discuss later).
There are numerous compounds in which additional
ligands such as CO or PR3 are present.
3- Nonclassically bonded compounds
In many orgenometallic compounds there is a type of
metal to carbon bonding that cannot be explained in terms of
ionic or electron-pair 8 bonds. One class comprises of the alkyls
of Li, Be, and Al that have bridging alkyl groups.
Here, there is electron- deficiency as in boron hydride
and the bonding is of a similar multicenter type.
A second, much larger class comprises compounds of
transition metals with alkenes, alkynes, benzene, and other ring
systems such as

11
 first the organo compounds of the main group elements is
considered, including the nonclassically bonded ones, and then
turn to the transition metal compounds.

SYNTHETIC METHODS:
There are many ways of generating metal to carbon
bonds that are useful for both nontransition and transition
metals. Some of the more important are as follows:
1- Reaction Between Metals and Alkyl or Aryl Halides
Probably the most commonly employed method is that
involving reaction between the metal and an alkyl or aryl halide.
Both lithium and magnesium metals react with organic halides,
provided that a suitable solvent such as diethyl ether is used:

(a)
for example

but- 1-yl bromide

12
 The reaction is normally carried out by adding the
halogen compounds, dissolved in ether, to the metal under an
atmosphere of dry nitrogen (Argon). In the case of magnesium a
little iodine may be necessary to initiate the reaction but once
started, with either metal it continues exothermically to
completion and the rate must be controlled carefully by adding
the halogen compound slowly.

Fig (1) : Synthesis of Grignard Reagents

13
 The synthetic applications of the magnesium compounds
were first realized and developed by Grignard and consequently
these alkyl or aryl magnesium halides are known as Grignard
reagent. Direct interactions of alkyl or aryl halides occur also
with Na, K, Ms, Ca, Zn and Cd.

2- Reaction between metal halides and other organometallic

compounds (use of alkylating agent)
The above compounds can be utilized to make
other organometallic compounds. The most important and
widely used are Grignard and lithium reagents. Aluminum and
mercury alky Is and certain sodium derivatives, especially
NaC5H5, are also useful alkylating agents .

Most nonmetal and metal halides or halide derivatives

can be alkylated in ether, or hydrocarbon solvents, for example

diethylcadmium
Organoborane may be similarly obtained

14
3- Interaction of metal or nonmetal hydrides with alkenes

or alkynes.
One of the best example for nonmetals, and one that
finds wide use in synthesis, is the hydroboration reaction

Carbonylation using CO results in the formation of

compounds in which carbon is "inserted" between the B and C

15
of the alkyl group. For transition metals and hydride complexes
such reactions are of prime importance in that many catalytic
syntheses involving transition metals (will discuss later) have as
an early step the reaction

4- Oxidative-addition Reactions:
The so-called oxad reactions where alkyl or aryl halides are
added to coordinatevely unsaturated transition metal
compounds generate metal - carbon bonds, eg.

(Wilkinson's catalyst) Chlorotris (triphenylphosphine) rhodium

trans-carbonylchorobis(triphenylphosphine) iridium
(Vaska's compound.)
d8(16 valence shell electrons) d6 (18 valence shell elec.)

16
The oxad to coordinatevely unsaturated metal complexes
of compounds with, C= C, C == C, and C =0, C=S and C = N,
can lead to M-C a bonds

CF2
Fe(CO)5 + 2CF2=CF2 (CO)4 Fe CF2 + CO
CF2 CF2

Ph3P C R
(PPh3)3Pt + RC RC
Pt + PPh3
Ph3P R

Coordinatively unsaturated compounds, whether transition

metals or not can generally add neutral or anionic nucleophiles
for example

but it is important to note that, even when they are electron-

rich, coordinatevely unsaturated species may show Lewis
acid as well as Lewis base behavior, for example,

17
When a complex behaves simultaneously as acid and base we
have the so-called Oxidative addition reaction, which can be
written generally as

The formal oxidation number of the metal atom increases by

two units. The reverse reaction can be termed reductive
elimination Oxad reactions have generally come to mean a
class of reaction of transition metal complexes in which
oxidation, i.e. an increase in formal oxidation number of the
central metal, is accompanied by an increase in the
coordination number.

5- Insertion Reactions (Migration of atoms or groups from

metal to ligand).
The concept of "insertion" is of wide applicability in chemistry
when defined as a reaction between two atoms initially bound
together:

Some representative examples are

R3S„NR2 + C02 R3SnOC(0)NR2 .
Ti (NR2)4 + 4CS2 Ti(S2CNR2)4.
(CO)5MnCH3 + CO (CO)5 MnCOCH3
SbCl5 + 2HC = CH Cl3Sb (CH = CHC1)2

(a) Insertion of unsaturated compounds, into M-H bonds

18
6- Elimination Reactions:
These are the reverse of insertion reactions. They involve
the elimination from appropriate compounds. Such as acyls,
carboxylate, sulfanates, azo compounds or hydrides of CO, C02,
S02, N2, H2, etc.. by action of heat or light with the concomitant
formation of M-C a bond

19
CHEMICAL CHARACTER AND SYNTHETIC USES OF
ORGANOMETALLIC COMPOUNDS
The chemical reactivity of organometallic compounds
depends in measure upon the nature of the metal concerned.
For highly electropositive metals, such as sodium, their
organic derivatives may be regarded as being highly ionic, that
is composed of separate ions.
Sodium acetylide in liquid ammonia, for example, will
contain (solvated) sod, and acetylide ions, Na+ and HC =C~. The
reactions of these compounds with, say halogenoalkanes, are
nucleophilic substitution reactions in which the acetylide ion
displaces a halide ion form the halogenoalkane.

HC C + R Hal HC CR + Hal-

Acetylide ions are powerful nucleophiles

1- Reactions with acids

Organometallic compounds of the more electropositive
metals, such as lithium, sodium, and magnesium, react even
with very weak acids to produce a hydrocarbon derived by
protonation of the organic group.

20
Even ethyl acetoacetate is a sufficiently strong acid to liberate
hydrocarbon from a Grignard or lithium reagent:

This type of reaction is useful on two principal counts. It some

times affords a method of hydrocarbon synthesis or a
convenient way of removing a halogen function from a
molecule.
2- Reaction with halogenalkanes.
Both organolithium compounds and Grignard reagents react
to produce hydrocarbons provided that the halide is
particularly reactive. Grignard reagents will not,
however, react with simple halogenoalkanes such as
bromoethane.

with acetylide the reaction is even more useful because, as well

as resulting in carbon- carbon bond formation, the reaction
yields products which are capable of further useful
transformation by virtue of the reactive acetylene group which
they contain.

21
HC CNa + C3H7I HC CC3H7 + NaI
Sod cetylide 1-iodopropane pentyne

H2/Pd H2O/H2SO4
HOH
CH3CH2C3H7 CH3COC3H7
pentane pentane-2-one
(methyl proplketone)

3- Reaction with Ketones and Aldehydes:

Organometallic compounds such as Grignard reagents and
organolithium compounds attack aldehydes and ketones at the
Carbonyl carbon, forming a new carbon-carbon bond. The alkyl
(or aryl) group departs from the metal with the bonding
electrons and is nacleophilic. We are dealing here with reaction
at a multiple bond and addition is observed rather than
substitution. The product is a metal alkoxide which is readily
hydrolysed by water to give an
CH3
H3C
HCl
C O + CH3MgBr H3C C OMgBr (CH3)3COH
(aq)
H3C
CH3 tertiary-butanol/
acetone a Tertiary alc.
CH3
H3C
HCl
C O + CH3MgBr H C OMgBr (CH3)3COH
(aq)
H
CH3 propan-2-ol/
acetaldehyde (secondary alc.)
H
H
HCl
C O + CH3MgBr H C OMgBr CH3CH2OH
(aq)
H
CH3 ethanol
formaldehyde (primary alc.)

22
Note that ketones lead to tertiary alcohols, and aldehydes to
secondary alcohols. Only formaldehyde, which is unique among

Carbonyl compounds, can give a primary alcohol.

Lithium compounds behave like the magnesium compounds:

4- Reactions with Acid Chlorides (RCOC1):

Acid chlorides have both a Carbonyl group and a reactive
carbon-chlorine group.
It is not surprising, therefore that Grignard reagents and
organolithium compounds affect both.
The chlorine is displaced in the first instance, by the
nucleophilic alkyl group, to yield a ketone which then rapidly
reacts further to give a tertiary alcohol.

23
For example:

The ketone is usually too reactive to be isolated, and this

reaction is therefore of no use for ketone synthesis.

Again, the product is tertiary alcohol!

24
6- Oxidation of Organometallic Compounds:
Most organometallic reagents, in solution or otherwise in an
inert, oxygen free atmosphere. Most are re oxidized.
Molecular oxygen, for example, can oxidize Grignard the
product contain an oxygen atom "inserted" between(and the
metal atom:

It is in fact, a magnesium alkoxide and hydrolysis c hydroxy

compound:

Oxidation of tnalkylboranes is very much more import, and this

is usually achieved with a solution of hydrogen

The product is an ester of boric acid (CH3BO3) or B(OH Like

most esters, these are readily hydrolysed by al products of
hydrolysis are boric acid and an alcohol

25
6- Oxidation of Organometallic Compounds:
Most organometallic reagents, in solution or otherwise in an
inert, oxygen free atmosphere. Most are re oxidized.
Molecular oxygen, for example, can oxidize Grignard the
product contain an oxygen atom "inserted" between(and the
metal atom:

It is in fact, a magnesium alkoxide and hydrolysis c hydroxy

compound:

Oxidation of tnalkylboranes is very much more import, and this

is usually achieved with a solution of hydrogen

The product is an ester of boric acid (CH3BO3) or B(OH Like

most esters, these are readily hydrolysed by al products of
hydrolysis are boric acid and an alcohol

26
6- Oxidation of Organometallic Compounds:
Most organometallic reagents, in solution or otherwise in an
inert, oxygen free atmosphere. Most are re oxidized.
Molecular oxygen, for example, can oxidize Grignard the
product contain an oxygen atom "inserted" between(and the
metal atom:

It is in fact, a magnesium alkoxide and hydrolysis c hydroxy

compound:

Oxidation of tnalkylboranes is very much more import, and this

is usually achieved with a solution of hydrogen

The product is an ester of boric acid (CH3BO3) or B(OH Like

most esters, these are readily hydrolysed by al products of
hydrolysis are boric acid and an alcohol

27
28
 ORGANO COMPOUNDS OF
THE MAIN GROUP ELEMENTS
We consider first the Organo compounds of the main group
elements, including the nonclassically bonded ones:
1- lithium Alkyls and Aryls
One of the major uses of metallic lithium, industrially and in the
laboratory is for the preparation of Organo lithium compounds
which in their reaction generally resemble Grignard reagents,
although they are usually more reactive
Methods of synthesis.
(a) They are prepared by direct interaction of the organic
halide, usually the chloride,
C2H5Cl + 2Li C2H5Li + LiCl (1)
in benzene or petroleum; ethers can be used but they are
attacked slowly by the lithium compounds.
(b) Metal hydrogen exchange
in benzene or petroleum ethers can be used but they are attacked
slowly by the lithium compounds.
(b) Metal hydrogen exchange
Li

n- C4H9Li + Fe n – C4 H10 + Fe

29
(c) Metal – halogen exchange

Br Li

n- C4H9Li + n – C4 H9Br +
N N

(d) Metal – metal exchange

2Li +R2Hg 2RLi + Hg
 n-butyl lithium in hexane, benzene, or ethers is commonly
used for such reactions.
 Methyl lithium is also prepared by exchange through the
interaction of n-C4H9Li and CH3I in hexane at low
temperatures, when it precipitates as insoluble white
crystals.
 Organo lithium compounds all react rapidly with oxygen,
being usually spontaneously flammable in air, with liquid
water and with water vapor.
 However, lithium bromide and iodide form solid complexes
and these solids are stable in air. Their stoichiometry are RLi
(LiX)1-6 (R = alkyl).
 Organolithium compounds that have properties-(solubility in
hydrocarbons or other nonpolar liquids and high volatility)-
typical of covalent substances.
 They are generally liquids or low-melting solids.
 Molecular association is an important feature of the alkyls in
both crystals and solutions.

30
 In solutions the nature of the polymerized species depends
on the solvent, temperature, and the steric nature of the
organic radical.
 In hydrocarbons MeLi, EtLi, n-PrLi and some others are
hexamers, but tert-butyl Li, which presumably bulky, is only
tetrameric.
 The alkyls and aryls also form complexes with other metal
alkyls such those of Mg, Cd, and Zn, for example.
2LiC6H5 + Mg(C6H5)2 Li2 [Mg(C6H5)4]
 reactions of lithium alkyls are generally considered to be
carbanionic in nature.
 Lithium alkyls are widely employed as stereospecific
catalysts for the polymerization of alkenes,

II- Organo-Sodium and Potassium Compounds.

These compounds are all essentially ionic and are not soluble to
any appreciable extent in hydrocarbons; they are exceedingly
reactive, sensitive to air, and are hydrolyzed vigorously by
water.
 Most important are the sod. compounds from acidic
hydrocarbons such as cyclopentadiene, indene, acetylenes,
and the like. These are obtained by interaction with metallic
sodium in THF or dimethylformamide [HCON Me2]
2 C5H6 + 2 Na 2 C5H5 Na+ + H2
RC  CH + Na RC C- Na+ + ½ H2

31
III – Magnesium
The organic compounds of Ca, Sr and Ba are highly ionic and
reactive and are not useful, but the magnesium compounds are
probably the most widely of all organometallic compounds.
 They are used very extensively in organic chemistry as well
as in synthesis of alkyl and aryl compounds of other
elements.
 They are of types RMgX (the Grignard reagents) and MgR2.
 The former are made by direct interaction of the metal with
an organic halid RX in a suitable solvent, usually an ether
such as diethyl ether or THF.
 The reaction is normally most rapid with iodides, RI, and
iodine may be used as an initiator.
 For most purposes, RMgX reagents are used in situ.
 The species MgR2 are best made by the dry reaction.
 HgR2 + Mg (excess) Hg + MgR2
 The dialkyl or diaryl is then extracted with an organic
solvent.
 Both RMgX, as solvates, and R2Mg are reactive, being
sensitive to oxidation by air and hydrolysis by water.
 The nature of Grignard reagents in solution is complex and
depends on the nature of the alkyl and halide groups and on
the solvent, concentration and temperature.
 Generally, the equilibria involved are of the type:

32
 X
RMg MgR 2RMgX R2Mg + MgX2
X

R X
Mg Mg
R X

Solvation occurs and association is predominantly by halide

rather than by carbon bridges, except for methyl compounds
where bridging by CH3 groups may occur.

 For crystalline Grignard reagents both the structures RMgX-

nS where n the number of solvent molecules, S, depends on
the nature of R, and R(S)Mg (-x)2 Mg(S)R have been
found. The Mg atom is usually tetrahedral coordinated.
 Zinc and cadmium compounds are similar to those of
magnesium but differ in their reactivities. The lower alkyls
of zinc are liquids spontaneously flammable in air. They
react vigorously with water.
 IV- Mercury:
 A vast number of organomercury is known, some of which
have useful physiological properties.
 They are of the types RHgX and R2 Hg.
 They are commonly made by reaction of HgCl2 and RMgX,
but Hg-C bonds can also be made in other ways discussed
below.

33
 The RHgX compounds are crystalline solids.
 When X form covalent bonds to mercury, for example, Cl,
Br, I, CN, SCN, or OH, the compound is a covalent nonpolar
substance more soluble in organic liquids than in water.
 When X is SO42- or NO3-, the substance is salt-like and
presumably quite ionic, for instance, [RHg]+ NO3 and
[RHg]2SO4 2-
 They are unaffected by air or water, presumably because of
the low polarity of Hg-C bond and the low affinity of
mercury for oxygen.
 They are photochemically and thermally unstable. In the
dark, mercury compounds can be kept for months.
 The decomposition generally proceeds by homolysis of the
Hg-C bond and free-radical reactions.
 All RHgX and R2 Hg molecules have linear bonds.
 The principal utility of dialkyl-and diaryl-mercury
compounds, and a very valuable one, is in the preparation of
other organo compounds by interchange reactions.
n
For example n/2 RnHg + M RnM+ Hg
2
This reaction proceeds essentially to completion with Li and Ca
groups, and with Zn, Al, Ga, Sn, Pb, Sb, Br, Se, and Te, but
with In, Ti and Cd reversible equilibria are established.
 Mercury released to the enviroment, as metal, for example,
by losses from electrolytic cells used for NaOH and Cl2
production, or as compounds such as alkylmercury seed

34
 dressing or fungicides, constitutes a serious hazard. This is a
result of biological methylation to give highly toxic
(CH3)2Hg or CH3Hg+.

Mercuration:
An important reaction for the formation of Hg-C bonds, and
one that can be adapted to the synthesis of a wide range variety
of organic compounds, is the addition of mercuric salts,notably
the acetate, trifluoroacetate or nitrate to unsaturated compounds
Mercuration of aromatic compounds occurs as follows:

HgNO 3 + HNO 3
+Hg (NO) 3)2

Hg OCOCH3
+ Hg (OCOCH 3)2 +CH 3COOH

HgOCOF 3
+CF 3COOH
+ Hg (OCOCF 3)2

Mercuric salts also react with alkenes in a reversible reaction

X
C=C + HgX2 C C
NO3 HgX
Boron:
There is an extensive chemistry of organoboron compounds.
 The trialkyl and aryl-borons are made from the halides by Li
or Grignard reagents and by hydroboration.

35
  The most important compound is sod tetraphenylbarate. Na
BPh4. This is soluble in water and is stable in weakly acid
solution, it gives insoluble precipitates with larger cations
such as K+, Rb+ or Me4N+, that are suitable for gravimetric
analysis.
Aluminum:
The alkyls of Al are of great importance because of their
industrial use as catalysts for the polymerization of ethylene and
propylene.
e.g. hydrocarbon solution of TiCl4 in presence of AlEt3
polymerize ethylene at 1atm pressure.
 They are also widely used as reducing and alkylating agents
for transition metal complexes.
The alkyls may be prepared by the reactions:
2 Al + 3R2Hg 2 R3Al (or [R3Al]2 + 3 Hg
RMgCl + AlCl3 RAlCl2, R2AlCl, R3Al.

Ziegler-Natta Polymerization

CH2R CH2R CH2R

CH2 CH2
C2H4
Ti Ti Ti
AlEt3 CH2 CH2

vacant site R
vacant site
CH2
Ti CH2
CH2

36
- The Ziegler-Natta polymerization system is heterogeneous,
and the active metal species is a fibrous form of TiCl3
formed in situ from TiCl4 and AlEt3.
-
- The second function of Alalkyl appears to be replacement of
one the chloride ions at the TiCl3 surface by an alkyl radical
derived from it, the surface Ti atom has one of its 6-
coordination sites vacant.
- The ethylene molecule becomes bound to the vacant site.
The alkyl group is then transferred to the coordination
ethylene.
- A further molecule of CH2-CH2 is then bound to the vacant
site and the process is repeated.
- An important extension of (Z-N-polymer) is the copoly-
merization of styrene, butadiene and dicyclopentadiene or
1,4-hexadiene to give synthetic rubbers.
- Vanadyl halides instead of titanium halides are then the
preferred catalyst.
Ge, Sn and Pb
 There is an exceedingly extensive chemistry of the group IV
elements bound to carbon.
 Some of the compounds, notably silicon-oxygen polymers
and alkyl-tin and- lead compounds, are of commercial
importance Ge-compounds have no uses.
 Essentially all the compounds are of the tetravalent
elements.

37
 For all four elements the compounds can generally be
designated R4-nMXn, where R is alkyl or aryl and X can be H,
Cl, O, COR/, OR/, NR2, SR/, Mn(CO)5, W(CO)3 (3-C5 H5),
etc.
 the most important compounds are (CH3)4 Pb and (C2H5)4
Pb, which are made in huge quantities for use as antiknock
agents in gasoline.
Phosphorus, As, Sb and Bi:
 There is an extensive chemistry of organo compounds,
especially of phosphorus and arsenic.
 This was developed largely because of the physiological
properties of these compounds.
 The so-called “organophosphorus” compounds that have
anti-cholinesterase activity and are widely used as
insecticides do not contain P-C bonds, but are P(v)
derivatives such as phosphates or thionates.
 Trimethylphosphine is spontaneously flammable in air, but
the higher trialkyls are oxidized more slowly.
 The R3MO compounds, which may be obtained from the
oxo halides as shown
(O)MX3 + 3 RMgX (O)MR3 + 3 MgX2
are all very stable.
 The trialkyl or alkyl-arylphosphines are usually liquids with
an unpleasant odor.

38
 The triarylphosphines are white crystalline solids reasonably
stable in air.
 Tertiary phosphines, arsines and stibines are all good -acid
ligands for d-group transition metals.
 Trialkyl and triarylphosphines,-arsines and-stibines
generally react with alkyl and aryl halides to form
quaternary salts:
R3 M + R / X [R3R/M]+ X-
 The tetraphenyl phesphonium and arsonium ions are useful
for precipitating large anions such as ReO4, ClO4, and
complex anions of metals.
 PPh3 as well as being an important ligand, is utilized in the
Wittig reaction for olefin synthesis.
[Ph3PCH3]+ Br n-butyl Li
Ph3P = CH2
quarternary alkylidenetriphenylphospherane (ylide)
This intermediate reacts very rapidly with aldehydes and ketones to

give zwitter-ionic compounds,

O
CH2P+Ph3
cyclohexanone
Ph3P = CH2
Which eliminate triphenylphosphine oxides under mild
conditions to give olefins
CH2
+ Ph3PO

 Alkylidenephosphoranes such as Me3P = CH2, Et3P = CH2,

Me2EtP = CH2 are all colorless liquids, stable for long
periods in an inert atmosphere.

39
40
ORGANOMETALLIC COMPOUNDS OF
TRANSITION METALS
Classification:
The compounds discussed in the following chapters are
classified by the organic ligands attached to the metal according
to the number of electrons which are formally considered to
arise from the ligand and which take part in the formation of
metal-ligand bond.
This classification is shown in the table below.
Table (1): A classification of organic groups which act as ligand
to T.M.
Name of class Example of organic group
No. of
electrons
1 Yl Alkyl or aryl group, compare Cl;
CN and H.
2 Alkene Ethylene, CO, PPh3.
3 Enyl -Allyl, nitrosyl
4 Diene Cyclobutadiene, butadiene
5 Dienyl -Cyclopentadicnyl C5H 5
6 6-C7H8 Triene Benzene, Cycloheptatriene
7 Trienyl -Cycloheptatrienyl
n-designate the number of ligand atoms (n) formally bound to
the metal the letter  stands for hapto from haptein meaning “to
fasten” thus - C5H 5 ligand is said to be pentahapto
cyclopentadienyl group.

41
 Table 2: Electron counting for -donor ligsnds
Electrons
Contributed Ligand Structure Example

2 2C2H4 H2C=C2 [PtCl3(C2H4)]-

trichloro(ethylene)platinate(1-)


 -C5H 5
Fe
2 OC
CO

 -cyclopentadienyl

CH Br
4  -C3H 5 Pd Pd
H2C CH2
Br
 -allyl
bis(3-allyl)di--bromodipalladium

4  -C4H 6 Fe(CO)3

 -butadiene 4-butadienetricarbonyliron

4  C5H6
Mo(CO)2
 -cyclopentadiene 2
4
dicarbonylbis( -cyclopentadiene)-
molybdenum
4  C8H6
Co(C5 H5 )

 -cyclooctatetraene (cot)
(1,2,5,6-4-cyclooctatetraene)
(5- cyclopentadienyl) cobalt
_____________________________________________________________

42
 Table 2: Electron counting for -donor ligsnds (Continued)
Electrons
Contributed Ligand Structure Example

4  C4H4

 -cyclobutadiene

4  C7H 7

 -cycloheptatrinyl

4  C7H8

trtrahaptonorbornadiene
2-
6  C4H 24 Fe(CO)3

 -cyclobutadiene tricarbonyl(4-cyclobutadiene) iron

6  -C5H 5 MO(CO)3Cl

 -cyclopentadienyl(Cp) tricarbonylchloro(5-cyclopentadienyl)

molybdenum

6  -C5H 6 +
Fe(CO)3
 -pentadienyl
tricarbonyl (5-pentadienyl)iron(1+)
________________________________________________________________

43
 Table 2: Electron counting for -donor ligsnds (Continued)
Electrons
Contribute Ligand Structure Example
d

6  -C6H6

 -benzene Cr

bis(benzene) chromium
+
6  -C7H 7 +

 -tropylium
Mo(CO)3

tricarbonyl(7-tropylium)-
molybdenum (1+)
6 6-C7H8
6-cycloheptatriene
Mo(CO)3
tricarbonyl(6cycloheptatri
ene)- molybdenum
6 6-C8H8
6-cycloheptatriene (cot)

Cr(CO)3

tricarbonyl(6cyclooctatetra
ene)-chromium
_______________________________________________________________
 The basis of the above classification is the 18-electrons
rule and it is appropriate to discuss this rule here.

44
The 18-electrons rule. (Effective Atomic Number (EAN) rule)
 The large majority of the transition metal complexes with
metal-carbon organic,-carbonyl or- hydride ligands isolable
at room temperature can be regarded as having 18 electrons
in their valence shell. This is the empirical basis of the rule
“a valence shell containing 18-electrons gives stable
complexes”.
 In order to test the application of the 18-electron rule to a
compound it is necessary to count the number of electrons
which are formally in the valence shell of the metal atom.
 This is most easily achieved in the following manner:
(a) Take the number of electrons in the valence shell of the
uncomplexed metal atom and add or subtract electrons
according to the total charge on the metal complex.
e.g. Fe+ cation had 7 electrons.
Fe0 neutral has 8 electrons.
Fe- anion has 9 electrons.
(b) Sum the number of electrons which the ligands formally
contribute to the metal, according to the classifiation of
ligand given above.
(c) Add this sum to the metal electrons from (a).

45
Examples:
1- [-C5H5 Fe(CO)2 C2H4]+
Fe+ 7
-C5H5 5
(CO)2 4
C2H4 2
------
18e
2- [Ni(CO)4]
Ni0 10
(CO)4 8
-----
18 e
3- Mn2(CO)10
Polynuclear carbonyls
Mn0 7
(CO)5 10
Mn-Mn covalent 1
bond -----
18 e

4- [-C3H5Fe(CO)2NO]
Fe0 8
(CO)2 4
NO 3
-Allyl 3
------
18 e

The Effective Atomic Number (EAN):

The effective atomic number (EAN) of a metal ion is calculated
by adding the electrons of the metal ion to those share with it
through coordination.

46
e.g. [Co (NH3)6]3+ the cobalt (III) ion has 24 electron plus the
six electron pairs from the ammonia molecules for a total of 36
electrons which is the configuration of krypton.
- The EAN concept has been particularly successful for the
metal carbonyls, which are thought to contain the metal with
the zero oxidation number and for some -complexes such
as ferrocene.
- In general EAN can be taken only as a rough gide. Most of
the complexes of Ni(II) give EAN values which are 34 (CN)
4 or 38 (CN) 6 rather than 36.
- The electron counting scheme is also called the rule of
eighteen in contrast to the usual rule of eight for “simple
compounds”.
- The rule of eight applies to main group elements for which S
and P are the only low energy orbitals to be filled.
- For transition metals the d orbitals are included in the
valence shell, since they are comparable in energy to the
filled S and P orbitals of the same quantum number.
- The energy of the d orbitals is lowered with increasing
nuclear charge through a transition series, so that after
several d electrons have been added the addition of ligand
electrons can complete a shell of 18 electrons.

47
Molecular and Electronic Structures of Carbonyls
The EAN Rule:
- Complexes of the transition metal with -acid ligands as
well as their organometallic complexes, generally obey the
EAN rule.
- Their stoichiometries and molecular structures usually can
be predicted and understood as arising from a tendency to
surround each metal with a full complement of 18 electrons.
- This is just another way of saying that the nd, (n+1)s and
(n+1)p orbitals all are valence orbitals in the transition
series, and that all their bonding capacity is used when the
18-electron configuration is reached.
- Figure (1) shows the changes in energy for the 3d, 4S and 4P
orbitals of the first transition series atoms.
- As you can see all orbitals become more stable as the central
part (V-Co), all the orbitals are of fairly similar energy, and
so all are available for bonding and the EAN rule is expected
to apply.
- As the end of the series is approached, the 3d and 4S orbitals
drop in energy faster than the 4P, until at Zn the 3d’s are part
of the atomic core and too stable to participate in bonding.
- Hence, we expect that Zn, (and the representative metals
beyond) should not obey the EAN rule. For Cu the
prediction is similar.
- For Ni(o) it makes no difference whether or not we consider
the d’s to be part of the core since they are filled completely

48
 whereas the 4S and 4P orbitals are still available for
bonding, leading to a prediction of 18 electrons around
Ni(o).
- As some orbitals disappear into the core toward the end of
the transition series, 16-and even 14-electron species
become more stable.

Increasing of 4P valence
binding energy
4S bond
3d
core
Ca Se Ti Cr Mn Fe Co Ni Cu Zn

Figure 1 The change in energy of the 3d, 4S and 4P orbitals of the

first transition series. (After C.S.G. Phillips and J.P Williams in
Inorganic Chemistry. Vol. II. Oxford, Oxford, 1966).
- Early in the series [before V(o)] the d orbitals are not all
energetically available for bonding, and hence the EAN
rule is not expected to hold.
- For the second and third transition series, similar trends
are anticipated. In short, we expect the EAN rule to be
valid toward the middle of the series for metals with low
or negative oxidation numbers.
- Increasing the oxidation number changes the slopes of
the binding energy versus atomic number curves and
increases their separation.

49
Examples:
(1)dicarbonyl(monohaptocyclopentadienyl)(pentahaptocycl-
opentadienyl) iron (II)
(5-C5H5) Fe (CO)2 (1-C5H5)
2CO = 4e

5-C5H 5 = 6e (3 -pairs)
Fe
1-C5H 5 = 2e (3 -pair)
CO CO
Fe2+ = 6e
_____
18 electrons

(2) bis (6-benzene) chromium Cr (C6H6)2

2 C6H6 = 6  pairs = 12e
Cr(o) = 6e Cr
_____
18 electrons

(3) [Mn(CO)4 (3-C3H5)

trihaptoallyl tetracarbonyl manganese (+1)
3- C3H 5 = 4e (2 pairs)
4CO = 8e (CO)3Mn
Mn+ = 6e
_____
18 electrons
3
(4) Co (CO)3 ( -C3H5)
tricarbonyltrihaptoallyl cobalt (+1) CO
3-C3H 5 = 4e (2 pairs) CO Co
8CO = 6e CO
Co+ = 8e
_____
18 electrons

50
(5) tricarbonyl (hexeahaptocycloheptatriene) chromium (o)
[(6-C7H8)(CO3)]
6 -C7H8 = 6e
3 CO = 6e
Cr(o) = 6e
Cr
-----
18 electrons OC CO
CO

(6) tricarbonyl(tetrahaptocycobutadiene) iron(II)

Fe(CO)3 (4-C4H4)
4-C4H42- = 6e
3CO = 6e Fe
2+
Fe = 6e OC CO
-------- CO
18 electrons
(7) tricarbonyl tropyliumMolybdeum (+1)
Mo(CO)3 (7-C7H7)
7-C7H7+ = 6e
3CO = 6e
+
Mo = 6e
--------
18 electrons

(8) carbonylpentahaptocycopentadienyl) trihapto cycloheptatrienyl)

iron (11)

Fe (5-C5H5) (CO) (3-C7H7)

3-C7H 7 = 4e
CO = 2e
Fe

 -C5H 5
5
= 6e CO
Fe2+ = 6e
-----
18 e

51
(9) tricarbonyl (1,2,5,6-tetrahahaptocyclo octatetraene) iron (o)
[Fe (4-C8H8) (CO)3]
4-C8H8 = 4e
3 CO = 6e
Fe
Fe (o) = 8e CO
CO
------- CO
18 e
(10) [Co ( – C5 H5) ( -C8H8)]
5 4

tetahaptocyclooctatetraenepentahaptocyclopentadienyl)cobalt(+
1)
4-C8H8 = 4e

 -C5H 5
5
= 6e Co
+
Co = 8e
--------
18 e
(11) tricarbonyl (hexahapto cyclooctatetraene)chromium(o)
Cr (6-C8H8) (CO)3
6-C8H8 = 6e
3 CO = 6e
Cr(o) = 6e Cr
-------- CO CO
CO
18 e
(12) tricarbonylpentahaptopentadienyl iron (+1)
[Fe(CO)3 (5-C5H5)]+
Fe(+1) = 7e+ +
3 CO = 6e Fe (CO)3

5-C5H 5 = 6e
_____
18e
(13) tricarbonyl(tetrahaptonorbornadiene) iron(o)
Fe(CO)3(4-C7H8)
Fe(o) = 8e
 -C7H8
4
= 4e
3 CO = 6e Fe
_____ CO CO
CO
18e

52
Two-electron ligands:
Classification:-
 The model 2-electron ligand is ethylene, and all olefinic
compounds which bind to a metal atom using one C = C
system can be treated as 2-electron ligands.
 Those olefines which have more than one C =C system but
which are unconjgated may be regarded as potential
chelating 2-electron ligands. e.g. cyclo-octa-1,5 diene is
calssfied as a two 2x electron ligand.
 These unconjugaed olefines are therefore distinguished from
conjugated olefins such as butadiene and cycloheptatriene
which are classified as 4- and 6-electron ligands
respectively.
 In table 2 examples are given of a variety of olefins which
act as 2-electron or n  2-electron ligands.
 The preparation of olefin-transition metal complexes
 Olefin-metal complexes are usually prepared by the
treatment of a metal complex with an olefin.
1- Displacement of solvent ligands
The treatment of many metal slats either in solution or in solid
state may be give smooth addition of the olefin to the complex.
-
 K2PtCl4 (aq) + C2H4 SnCl2 K+[C2H4PtCl3] . H2O
Cat
yellow crystals zenise’ salt

53
 CH2 CH2

SnCl2 CH2 Cl CH2

RhCl3 (aq) + C2H4 CH2 Rh Rh
Cat Cl CH2
CH2
CH2
bis-ethylene rhodium.

2- Preparation from metal carbonyls

 many metal carbonyls undergo easy replacement of some of
their carbon monoxide ligands. Cl

 [Rh (CO)2 Cl]2 + 2 C8H12 Rh Rh

Cl
 Irradiation of solutions of metal carbonyls in the presence of
an olefins is frequently a very good method of effecting
substitution of the carbonyl ligands.
 C2H4 + C5H5 Mn (CO)3 petrol.
U.V C5H5 Mn (CO)2 C2H4+CO

3- Less common preparative routs

Ligands other than carbon monoxide which may be displaced by

olefins include the labile ligand benzonitrile.
H H

e.g (C6H5CN)2PdCl2 + C7H8 + 2 C6H5CN

Pd

Cl Cl

54
 (MrCN)3 W(CO)3 triene (triene) W (CO)3 or + MeCN
or diere
 and even benzene (diene) W (CO)3

C7H8 H

H
Cr Cr
CO
CO
CO CO CO CO

C8H12
Ni
COD
Ni

A description of the bonding of 2-electron ligands to

transition metals:
 Ethylene will serve as an example of a typical 2-electron
hydrocarbon ligand.
 Ethylene, like carbon monoxide and tertiary phoshines
belongs to that class of ligand which does not often co-
ordinate readily with traditional acceptor molecules (Lewis
acids, e.g BF3), but which forms quite stable complexes with
transition metals which have some available d-electrons.
 It is postulated for ligands like ethylene that boning with the
metal involves both a simple -co-ordinate link and also a
back-donation of the metal electrons to the ligand.
 The -co-ordinate bond is the reason for the classification of
ethylene as a 2-electron ligand
e.g Zeise’s salt, K+[C2H4PtCl3]-

55
 C C

Cl

Pt
Cl
Cl
Structure of the anion [C2H4 PtCl3]-

56
General comments on 2-electron ligands
 The similarity between the carbonyl- and ethylene-metal
bond has been noticed earlier and indeed there is
considerable analogy between the chemistry of metal
cabonyls and metal- olefin complexes.
 Thus ethylenic ligands frequently complex with metals
which are in low oxidation state and which are formally
rich in electrons.
 Of course, filled d orbitals of suitable energy are required
for back-donation to the olefin ligand.
 For this reason olefin complexes are not found with the
higher oxidation state complexes e.g the higher chlorides
of the group IV-VII metals.
 In many complexes, the stability of the olefin-metals bond
depends markedly on the other ligands attached to the
metal. Copper (I) chloride forms more stable complexes
than copper (I) bromide whilest for the complex anions
[C2H4PtX3]-, the stability of the ethylene-platinum bond
falls in the order
X = Cl > Br > I > NO2 > SCN > CN.
 Olefin-metal complexes are frequently labile, especially
those of copper, Ag and Au, and treatment of most olefin-
metal complexes with ligands such as tertiary phosphines
result in displacement of the olefin.

57
Metal Carbonyls : Carbon Monoxide Complexes
 The most important -acceptor ligand is CO.
 Many carbonyl complexes are of considerable structural
interest as well as of importance industrially and in
catalytic and other reactions.
Mononuclear Metal Carbonyls:
 The simplest carbonyls are of the type M(CO)x (see
table).
 The compounds are all hydrophobic volatile and soluble
to varying degrees in nonpolar liquids.
Polynuclear Metal Caronyls
 There are numerous polynuclear carbonyls that may be
homonuclear for example Fe3(CO)12 or heteronuclear for
example Mn Re (CO)10.
 In these compounds there are not only linear M-C-O
groups but also either metal-metal bonds alone or M-M
bonds plus bridging carbonyl groups.
O OC M
C
M M M M
doubly bridging triply bridging

 The doubly bridging types occur fairly frequently and

always in conjunction with an M-M bond.
 Bridging CO groups very often occur in pairs as
O
C
M M
C
O
58
 Any pair of bridging CO groups can only be regarded as
an alternative to a nonbridging arrangement with two
terminal groups as: O
C

M
M
C
O
 The relative stabilities of the alternatives appear to depend
primarily on the size of the metal atoms.
 The larger the metal atoms size the greater is the
preference for a nonbridged structure .
 Thus in any group the relative stability of nonbridged
structures increases as the group is descended. (e.g.
Fe3(CO)12 has two bridging CO’s while Ru3 (CO)12 and
Os3 (CO)12 have none).
 The generalization concerning metal atom size also
covers the trend horizontally in the periodic table. Thus,
the large Mn atoms forms only the nonbridged (OC)5Mn-
Mn(CO)5 molecule whereas the dinuclear cobalt carbonyl
CO2(CO)8 exists as an equilibrium mixture of the bridged
and nonbridged structures. (see the Figure).

59
60
 Table (3) : Some Representative Metal Carbonyls and Carbonyl Hydrides
Compound Color and form Structure Comments
A. Mononuclear Carbonyls
V(CO)6 Black crystals: dec. Octahedral Yellow-orange
70°;sublimes solution;
in vacuun paramagnetic(Fe-)
Сг(СО)б Colorless crystals; Octahedral Stable to air;

Мо(СО)6 all sublime in dec. 180-200

W(CO)6 vacuum

Fe(CO)5 Yellow liquid; tbp Action of uv gives

mp-22° Fe(CO)9
bp 103°

RU(CO)5 Colorless liquid; tbp (by ir) very volatile and

mp-22° different to prepare

Ni(CO)4 Colorless liquid; Tetrahedral very toxic; musty

mp-25° smell; flammable;
bp-43° decomposes
readily to metal
B. Polynuclear Carbonyls

Мп2(СО)10 yellow solid the Mn-Mn bond

Subl. 50°(10"2mm) Mn2(CO)10 is
Reactive

Fe2(CO)9 gold solid very inscluble and

nonvolatile

Fe2(CO)12 green-black solid moderately soluble

Mp- 140-150
Decomp.

61
 Table (3) : Some Representative Metal Carbonyls and Carbonyl
Hydrides (Count.)

Compound Color and form Structure Comments

Rll4(CO)12 brick red solid Useful reagent for
Mp 150° decomp. many carbonyl
Subl. 65°(10"2mm) rhodium compounds

C. Car bony I Hydridesa

HMn(CO)5 Colorless liquid Octahedral Stable at 25°, weak acid

Mp-25° Uncertain  = 21.1
Decomp.-10°. weak acid
H2Fe(CO)4 yellow liquid,  = 21.1
Colorless gas
Mp-70°

H2Fe3(CO)11 Dark red liquid Uncertain

HCo(CO)4 Yellow liquid Distorted tbp Decomp. above mp

Colorless gas strong acid
Mp-20°  = 20

 value is position of high-resolution proton magnetic resonance

line in parts per million referred to tetramethylsilane reference
as 10.00

62
PREPARATION OF METAL CARBONYLS
• Many metals react directly with CO when prepared in a highly
dispersed form, the most common carbonyls prepared by this
way are Ni(CO)4 and Fe(CO)5,
a) Finely divided nickel will react at room temperature.
b) An appreciable rate of reaction with iron requires elevated
temperature and pressures.
• In general, carbonyls are formed when metal compounds are
reduced in the presence of CO.
• Usually high pressures (200-300 atom) of CO are required.
• In some cases, CO itself serves as the only necessary reducing-
agent, e.g
Re207 + 17CO Re2(CO)10 + 7C02
but usually an additional reducing agent is needed, typical ones
being H2, metals such as Na, Al, Mg, Cu, or, compounds such as
trialkylaluminium.

250-300 atm.
- 2 CoCO3 + 2H2 + 8 CO 120-150
Co2(CO)8 + 2CO2 + 2H2O

(C2H5)3Al
- 2 Mn (ac ac)2 + 10CO Mn2(CO)10
C6H5MgBr
- CrCl3 + 6CO Cr(CO)6

Bonding in Linear M-C-O group

It is possible to formulate the bonding in terms of a resonance
hybrid (a,b),
M" C+ = O : M - C = O:
(a) (b)

63
A molecular-orbital formulation is more detailed and accurate.
- There is, first, a dative overlap of the filled carbon cr orbital (i.e in
which the lone pairs of electrons on the C atoms interact with
vacant metallic orbitals)
(c) M+ C =O: M C=O :

and, second, a dative overlap of a filled d π or hybrid d p π metal

orbital with an empty antibonding p π orbital of the carbon monoxide
(in which filled metallic d-orbitals interact with low-lying vacant
antibonding n* orbitals of the CO group)

(d) M + : C = O: M C=O :

(d) M + :C=O: M :C=O:

(c) The formation of the carbon metal a bond using an

unshared pair on the C atom (c)

(d) The formation of the metal carbon n bond (d)

Bonding mechanism
- This bonding mechanism is synergic, since the drift of metal
electrons into CO orbitals will tend to make the CO as a whole
negative and, hence to increase its basicity via the σ orbital of
carbon; also the drift of electrons to the metal in the a bond

64
tends to make CO positive, thus enhancing the acceptor strength of
the π orbitals. Thus, the effects of σ-bond formation strengthen the π
bonding and vice versa. - The main lines of physical evidence
showing the multiple nature of the M-CO bonds are bond lengths and
vibrational spectra.

As the extent of back-donation from M to CO increases, the M-

C bond becomes stronger and the C=O becomes weaker. Thus
the multiple bonding should be evidenced by shorter M-C and
longer C-O bonds as compared with M-C single bonds and C = O
triple bonds, respectively.

Vibrational Spectra of Metal Carbonyls:

Infrared spectra have been widely used in the study of metal
carbonyls since the C-O stretching frequencies give very strong
sharp bond well separated from other vibrational modes of any other
ligands that may also present.
The CO molecule has a stretching frequency to 2143 cm-1 Terminal
CO groups in neutral metal carbonyl molecules are found in the
range 2125-1850 cm-1.
The most important use of IR spectra of CO compounds is in
structural diagnosis, where bridging and terminal CO groups can be
recognized.
For terminal M-CO, the frequencies of C-O stretches range from
1860 to 2125 cm-1 but for bridging CO groups the range is 1750-
1850 cm-1.

65
- When changes are made that should increase the extent of M-C
back bonding, the CO frequencies are shifted to even lower
values.
- Thus, if some CO groups are replaced by ligands with low or
regligible back-accepting ability, those CO groups that remain
must accept more d n electrons from the metal to prevent the
accumulation of-ve charge on the metal atom.
e.g Cr(CO)6 frequency 2000 cm-1
Cr(CO)3(dien) ,, 1900 and 1760 Cm-1
Dien = NH (CH2 CH2NH2)2

Similanly in V(CO)6 where more -ve charge must be taken from

the metal atom a band is found at 1860 cm-1 corresponding to the
one found at 2000 cm-1 in Cr(CO)6. Conversely, a change that would
tend to inhibit the shift of electrons from metal to CO σ orbital such
as placing a +ve charge on the metal should cause the CO
frequencies to rise.
e.g. Mn(CO)6, ~ 2090 Mn (Dien)(CO)3, -2020, ~ 1900 Cr(CO)6, ~
2000 Cr dien (CO)3, ~ 1900, ~ 1760 V(CO)6, ~ 1860. The frequency
of terminal CO stretches can be quite low if:
a) There are a number of ligands present that are good donor but
poor π -acceptors, or
There is a net -ve charge on the molecule. In either case, back-
donation to CO group becomes very extensive thus increasing
the M-C bond orders, decreasing the C-O bond orders and
driving the CO stretching frequencies down.

66
Reactions of Metal Carbonyls:
• The variety of reactions of various carbonyls is so large that only
a few types can be mentioned.
• Fig (A) gives an indication of the extensive chemistry that any
individual carbonyl typically has.
• The most important general reactions of carbonyls are those in
which CO groups are displaced by ligands, such as PX3, PR3
P(OR)3, SR2, NR3, OR2, RNC, etc. or unsaturated organic
molecules, such as CeH6 or cycloheptatriene.
• Another important general reaction is that with bases (OH-, H-,
NH2) leading to the carbonylate anions.
THF
e.g. C02(C0)8 + 2Na/Hg 2Na[Co(CO)4]
Fe (CO)5 + 3NaOH(aq) THF Na[HFe(CO)4] (aq)+ Na2C03(aq)+H2O
THF
Mn2(CO)10 + 2Li 2Li [Mn(CO)5]
• Substitution reactions may be proceed by either thermal or
photochemical activation. Generally in photochemical process
involves first expulsion of a CO group after absorption of a photon,
followed by entry of the substituent into the coordination system.
Cr(CO)6 ^ > Cr(CO)5 + L Cr (CO)5L
Carbonylate anions and Carbonyl Hydrides
Carbonylate anions are formed when carbonyls are treated with
aqueous or alcoholic alkali hydroxide or with amines, sulfoxides, or
other Lewis bases, when M-M bonds are cleaved with sodium or
when certain carbonlys are refluxed with salts in an ether, e.g. as
mention above.
The stoichiometrics of the simpler carbonylate ions obey the nobel-
gas formalism, (octet configuration). Most of them are readily
oxidized by air.

67
The alkali-metal salts are soluble in water from which they can be
precipitated by large cations such as [Ph4As]+
There are also many polynuclear species those of iron have been
much studied. They are obtained by reactions such as
Fe2 (CO)9 + 40H- [Fe2(CO)8]2- + 2H2O+CO

H2O
Fe(CO)5 + Et3N [Et3NH][HFe3(CO)11]
80 oC

- An important general reaction of carbonylate anions or substituted

carbonylate ions is with halogen compounds.
- By this reaction M-C or M-M bonds can be formed.
- Typical examples are:

- Mn(CO) + C1CH2CH = CH2 — (CO)5MnCH2CH = CH2 + CI-

- Fe(CO) + 2Ph3PAuCl (Ph3PAu)2 Fe (CO)4 + 2CI-

Co(CO)4 +Mn(CO)5Br (OC)4 CoMn(CO)5 + Br-

Carbonyl hydrides:
In some cases, hydrides corresponding to carbonylate anions can be
isolated. See table
- carbonyl hydrides are usually rather unstable.
- They can be obtained by acidification of appropriate alkali

carbonylates or in other ways.

e.g NaCo(CO)4 + H+aq HCo(CO)4 + Na+ (aq)

NaBH4
Fe(CO)4I2 + H2 H2Fe(CO)4
in THF

68
 200 atm
Mn2(CO)]0 + H2 2HMn(CO)5
o
200

50 atm
CO+4CO+1/2H2 HCO(CO)4
150o

The hydrides are slightly soluble in water where they behave as

acids, ionizing to give the carbonylate ions.
H Mn(CO)5 = H+ + [Mn(CO)5] pK ~ 7
H2Fe(CO)4 = H+ + [HFe(CO)4r pK, ~ 4
[HFe(CO)4]" = H+ + [Fe(CO)4]2" pK2 ~ 13
HCo (CO)4 = H+ + [Co(CO)4]" strong acid.
The carbonyl hydrides have sharp M-H stretching bands in the ir and
proton magnetic resonanc (PMR) at very high x values (very low 8
values). The hydrogen atom occupies a regular place in the
coordination polyhedron and the M-H distances are approximately
equal to the values expected from the sum of single-bond covalent
radii.
A good example is afforded by the structure of HMn(CO)5.

O
C
97
CO CO
Mg

CO CO
H
1.6 A

69
Carbonyl Halides and Related Compounds:
Carbonyl halides, Mx(CO) yXz, are known for most of the elements
forming binary carbonyls and also for Pd, Pt, Au, Cu1, and Ag1.
They are obtained either by the direct interaction of metal halides
and carbon monoxide, usually at high pressure, or by the cleavage
of polynuclear carbonyls by halogens:

40o in Pet/120o
Mn2 (CO)10 + Br2 2Mn(CO)5Br [Mn(CO)4Br]2+2CO
CO/150 atm

200o
RUI3 + 2CO [Ru(CO)2I2]n + ½ I2
atm

2PtCl2 + 2CO [Pt(CO)Cl2]2

Carbonyl halide anions are also known; they are often derived by
reaction of ionic halides with metal carbonyls or substituted
carbonyls:

diglym
M(CO)6 + R4N+X- R4N+[M(CO)5X]-+CO (M=Cr,Mo,W)

Mn2(CO)io + 2R4N+X- (R4N+)2[Mn2(CO)8X2]2-+2CO

70
 Table (4) Some examples of carbonyl halide complexes
Comp. From m.p.(c) Comment
Loses CO at 120 in organic
Pale yellow
Mn(CO)sCl Sublimes solvents; can be substituted
Xtals
by pyridine,..etc.
Halogen bridges cleavable
[Re(CO)4Cl]2 White Xtals Dec >250 by donor ligands or by
CO (pressure).
Halide bridges cleavable
[RU(CO)2I2]n Orange Stable>200
powder by ligands.

[Pt(C0)Cl2]2 Yellow Xtals 195; sublimes Hydrolyzed H20; PC13

replaces CO.

Dimeric or polymeric carbonyl halides are invariabley bridged

through the halogen atoms and not by carbonyl bridges, e.g.
CO CO
OC I CO Cl Cl CO
Re Re Pt Pt
OC I Cl
CO Cl Cl
CO CO

The halogen bridges can be broken by numerous donor ligands

such as pyridine, substitute phosphine isocyanides,..etc. as in the
following reaction:

CO Cl
OC CO CO
I CO OC OC I
2 Py I 2Py
Mn Mn 2 2
Mn Mn
OC I CO OC Py OC Py
CO CO CO CO

71
CARBON MONOXIDE ANALOGS
1- Isocyanides Complexes
An isocyanides , R-C≡ N, is very similar electronically to
:O≡C: , and there are many isocyanide complexes analogous
to metal carbonyls .
Isocyanides can occupy bridging as well as terminal
positions
e.g. Cr(CNPh)6 , (red) [ Mn(CNCH3)6] ( white)
Co(CO)(NO)(CNC7H7)2 ( orange) all soluble in C6H6
Isocyanides generally appear to be stronger σ donors than
CO, and various complexes such as
[ Ag(CNR)4]+ , [Fe(CNR)6]2+ and [Mn (CNR)6]2+
are known; derivatives of this type are not known for CO.
- However ,the isocyanide are capable of extensive back
acceptance of π - electrons from metal atoms in low
oxidation states.
- The C atom in CO has available low energy 2p orbital

72
 2p orbital

- This is indicated qualitatively by their ability to form compounds

such as Cr(CNR)6 and Ni(CNR)4, analogous to the carbonyls and
more quantitatively by C=N stretching frequencies which, like
CO stretching frequencies are markedly lowered when the ligand
acts as π -acid.

2- Dinitrogen Complexes: (N2)

The fact that CO and N2 are isoelectronic has led to speculation as
to the possible existence of M-NN bonds analogous to M-CO but
it was only in 1965 that the first example, [Ru(NH3)5N2]Cl2 was
reported.
- A bridging N2 ligand is formed in the reaction

Zn/Hg
[Ru(NH3)5 Cl]2+ {[Ru(NH3)5]N2]4+}
N2

73
- The terminal-type N2 ligands have strong IR bands in the range
1930-2230 Cm-1 (free N2 ~ 2330 Cm-1) that may be used
diagnostically.
- The bonding in M-N2 groups is similar to that in terminal M-CO
groups.

- The same two basic components, M N2 a donation and

M N2 -acceptance, are involved.

Donor Complexes of Group V and VI Ligands:

Trivalent phosphorus, arsenic, antimony compounds as well as
divalent S and Se compounds can give complexes with T.M. These
donors are quite strong Lewis bases and give complexes with Lewis
acids.
In P(CH3)3 the P atom uses four 3S3P3 hybrid orbitals, 3 for
bonding with the C atoms of the CH3 groups, and one for the
lone plair (b); its 3d and 4S orbitals are empty.

In [Pt Cl2 {P(CH3)3}2] the P atom of each P (CH3)3 ligand donates

its lone pair to Pt(II), in a a P Pt bond involving the
3
overlap of the 3S3P hybrid orbital of P with an empty 5d 6S 6P
hybrid (square planar) orbital of Pt (II) (c).

At the same time one of the empty M orbital of P overlaps with one
of the filled 5d orbitals of Pt (II) (d).
The electron density of the resulting Pt P bond is
shown in (e).

74
It may be mentioned that the  Pt P bond involves the empty
3d orbitals of phasphorus, rather than the empty 4S of slightly lower
energy, because d orbitals extend much farther from the nucleus and
therefore can form more efficient overlap with d orbitals of Pt (II).
- A metal ligand n bond requires that the metal have
available some outer electrons not belonging to a closed shell; the
metals which have the greatest tendency to act as n donors are those
in the second half of the transition series (d6, d7, d8 and d9 system).
- Based on it data an extensive series of ligands involving group V
and VI donor atoms can be arranged in the following order of
decreasing -acidity
-CO~PF3>PCl3~AsCl3~SbCl3>PCl2(OR)>PCl2R>PCl(OR)2> PC1R2

75
Nitric Oxide Complexes:
The NO molecule is similar to CO except that it contains one more
electron, which occupies n orbital.
- Consistent with this similarity CO and NO form many
comparble complexes although, as a result of the presence of the
additional electron, NO also forms a class (bent MNO) with no
carbonyl analogs.
Linear, Terminal MNO Groups:
We have seen that the CO group reacts with a metal atom that
presents an empty σ orbital and a pair of filled d π orbitals, to give a
linear MCO grouping with a C Μ σ bond and a significant
degree of Μ C π bonding.

The NO group engages in an entirely analogous reaction with a metal

atom that may be considered, at least formally, to present an empty σ
orbital and a pair of d π orbitals containing only three electrons.

76
The full set of four electrons for the Μ d π π*(ΝΟ) interactions
is thus made up of three electrons from Μ and one from NO.
In effect, NO contributes three electrons to the total bonding
configuration where CO contributes only two.
Therefore the ligand NO can be regarded as a three electron donor
in the same sense as the ligand CO is considered a two electron
donor.
This leads to the following useful general rule concerning
stoichiometry,
'Three CO groups can be replaced by two NO groups" examples of
pairs of compounds so related are
Fe (CO)5 , Fe(CO)2 (NO)2
Mn (CO)4NO , Mn (CO) (NO)3
Co(CO)3 NO , Co (NO)3

77
 Et
Et
S
S
(OC)3 Fe Fe(CO)3 (NO)2 Fe Fe(NO)2
S
S
Et
Et

- Structural data suggest that under comparable circumstances M-

CO and M-NO bonds are about equally strong, but in a chemical
sense the M-N bonds appear to be stronger, since substitution
reactions on mixed carbonylnitrosyl compounds typically result
in displacement of CO in preference to NO.
- For example Co(CO)3 NO reacts with R3 P, X3P, amine and RNC
ligands, invariably to yield the Co(CO)2(NO)L product.
- The NO vibration frequencies for linear MNO groups substantiate
the idea of extensive M to N n bonding, leading to appreciable
population of NO n orbitals.
- Nitric oxide has its unpaired electron in a n orbital; the N-0
stretching frequency is 1860 Cm-1. For typical linear MNO group
in molecules with small or zero charge, the observed frequencies
are in the range 1800 to 1900 Cm-1.
This indicates the presence of approximately one electron pair
shared between metal d n and NO * orbitals.

Bent, terminal MNO Groups:

It has long been known that NO can form single bonds to univalent
groups such as halogens and alkyl radicals, affording the bent
species.

78
 N=O and N=O
X R

- Metal atoms with suitable electron configurations and partial

coordination shells may bind NO in a similar way.
- This type of NO complex is formed when the incompletely
coordinated metal ion, LnM, would have a t2g6 eg1 configuration,
thus being prepared to form one more single c bond.
- The M-N-0 angles are in, or near, the range 120 to 140°.
- Typical compounds are [Co(NH3)5NO]Br2 and IrCl2(PPh3)2 NO.

Bridging NO Groups:
These are less common than bridging CO groups, but well
established cases of both double and triple bridges are known.
- As in carbonyls, the bridging NO frequencies are at lower
frequencies than terminal ones.
- Bridging NO groups are also to be regarded as three-electron
donors.
The doubly bridging ones may be represented as

O
N
M N=O
M
N
O

Where the additional electron required to form two metal-to-

nitrogen single bonds is supplied by one of the metal atoms.

79
The situation is formally analogous to that for bridging halogen
atoms

Three-Electron Ligands:
• Hydrocarbon ligands which rc-bond to a transition metal by a
conjugated system and which contribute three electrons in the
formation of the ligand-metal bond are called π -enyl ligands.
(Also called π -allylic ligands).
• The simplest 3-electron ligand is the -allyl group, -C3H5.
Preparation of π -enyl complexes:

There are several general routs available.

1- From ally! Grignard regents.

Pure π -allyl complexes are best prepared by treatment of
suitable metal salts with allyl Grignard reagents such as freshly
prepared ally magnesium bromide.

Et2O
2C3H5MgBr + NiCl2 Ni
-10o

80
2- From allyl halides and allyl alcohols.

Allyl halides react with a variety of anionic metal complexes forming

-allyl metal bonds

allyl halides and alcohols will also react directly with metal
compounds,
e-g

81
 'The preparation of some π -allyl complexes from allyl
halides"
3- From olefins
The formation of π -enyl complexes from a mono-olefin
probably proceeds via the prior formation of an unstable
olefin- metal compex, followed by the loss of a hydrogen
atom. The reaction may be compared to that of allyl
halides which lose the halogen. Examples:

H2 C
Cl
MeHC Pd Cl
2CH2 =CHCH3 + 2PdCl2
Cl Pd
Cl CHMe
proplene
CH2
[ -C3 H5 PdCl]2
-2HCl

4- From allenes
Treatment of bis-benzonitrile palladium dichloride with allene
affords a variety of π -enyl complexes depending on the
stoicheiometry of the reaction, and on the solvent.

• The addition of the allene to the palladium chloride complex is

reversible in so for that treatment of 2-chloropropenyl complex,

82
 i.e-where R, Rv = CI with tertiary phosphines such as Ph3P gives
allene
e-g
Ph3 P
[ π -CH2-CCl-CH2PdCl]2 (Ph3P)2PdCl2 +CH2= C= CH2
allene
Bonding in Aallyl metal Compounds
- The bonding situation between the rc-ally group and the metal is a
little more complicated than with olefins.
The lowest energy molecular orbital of the allyl anion is able to form
a strong a bond with an empty d orbital of the metal (hybride) while
the filled nonbonding orbital may overlap with the empty dxy metal
orbital. Further bonding may occur between the empty antibonding
allyl orbital and the filled dx2-y2 orbital.

The three ρ π orbitals of the ally group combine to form three

MO's

83
 The chemistry of particular π-enyl complexes.
• π-Enyl complexes differ widely in their properties;
• these also depend markedly on the other ligands attached to the
metal.
• the nitrosoyl ligand can also act as 3-electron ligand.

• π-Enyl complexes may exhibit versatile catalytic properties.

Cyclo-oligomerization of Buta-1,3 diene by Ni-PR3 Compounds

Some of the most elegant of recent work in the field of
homogeneous catalysis has been done by Wilk and his co-workers

• Treatment of bis- π -allyl nickel with butadiene, gives

cyclododecatriene nickel, a volatile blood-red crystalline
compound

84
larg range ketone present as:
- Tibetan Musk
- Deer-Civet-Cat
- Chanal No 5 one of the most
expensive perfume in the world
(a) Pure π-allyl complexes:
Examples of the known pure π-allyl metal complexes are given
below

VA3 CrA3 FeA3 CoA3 NiA2

ZrA4 NbA4 MoA4 RhA3 PdA2
TaA4 WA2 PtA2
A represents π-C3Η5

 The complexes (π-C3Η5)2Μ, where Μ = Ni, Pd or Pt,

show a decrease in their reactivity and catalytic properties,
and an increase in thermal stability with increasing atomic
weight of the metal.
 The complexes (π-C3Η5)2Μ may be assumed to have a
sandwich structure as found for bis- π -2-methyl allyl
nickel.
 (b) π-Enyl compelxes nickel, palladium and platinum
 The π-enyl complexes of nickel and palladium constitute a
large proportion of the known π-enyl complexes.

85
  The palladium complexes in particular are readily
prepared and the majority are easily handled in air at room
temperature
 The reactivity of π-enyl complexes varies widely.
 The very high reactivity of bis-π allyl nickel is shown by
the displacement reaction given below

CO PR3
dially= Ni(CO)4 Ni Ni(PR3)4

air HCl Cl
Ni Ni
Ni oxides
C4H6 Cl
-40o

warm
Ni Ni

86
Five-electron Ligands:
• Hydrocarbon ligand which formally contribute five electron when
bonding to a metal are called "Dienyl" ligands.

Cyclopentadienyl metal complexes:-

• a-Cyclopentadienyl transition metal Complexes:
• Cyclopentadiene is a weak acid (pKa ~ 20) and with strong bases
• forms the cyclopentadienide ion C5H5-

Classification and nomenclature:

The cyclopentadienyl radical C5H-5, forms three distinct classes of
complexes with transition metals.
1- -cyclopentadienyl complexes: are those which contain the
cyclopentadienyl ring essentially covalently bonded to the metal,
the metal being situated below the plane of the carbon atoms and
usually equidistant from the five equivalent carbon atoms.
2- In a few complexes the cyclopentadienyl radical may bind to the
metal by only one carbon atom via a covalent 2-electron bond
affording a-cyclopentadienyl complexes.
The third class consists of the cyclopentadienides which behave
chemically like the essentially ionic alkali metal cyclopentadienids.

87
Preparation:-
• The general method for synthesizing metal complexes is the
reaction of this ion with a metal halide or other complex,

e-g
HTF - +
C5H6 + Na C5H5 + Na + 1/2 H2

HTF
2 C5H5 + NiCl2 ( - C5H5)2Ni + 2 Cl -
• Two other methods are:
(a)The use of C5H5 π, which is insoluble in water stable and easily
stered:

and (b) the use of a strong organic base as proton acceptor,

Bonding in η5 - C5Η5 Metal Compounds:

- An MO treatment gives a good description of the bonding.
The main source of bonding is the overlap between the dyz and dz
orbitals of the metal atom with the ρπ orbitals of the ring or rings.

88
Figure (3) shows the dxz orbital overlaps; that of the dyz orbital is
precisely equivalent but occurs in the plane perpendicular to that
shown.
- because these two mutually perpendicular bonds are equivalent,
the rings are able to rotate freely about the axis from the metal to the
ring center.
- Alkyne Complexes:
Acetylenes are similar in their behaviour to the ethylene and CO
ligands
Thus we have the reactions:

89
One –electron ligands
A 1-electron ligand occupies essentially only one co-ordination
position on the metal and therefore has less influence on the
chemistry of complexes containing it than those organic ligands
which occupy several co-ordination positions and whose bonding
involves a large proportion of metal electrons .
Classification of 1-electron ligands:
The following main classes of 1-electron ligands may be recognized
and they are considered separetely .
I- ( 1 ) Hydrocarbon alkyl and aryl complexes, M-Rh .
(2) Hydrocarbon acyl complexes, M- CORh .
(3) σ –Alkenyl complexes
(4) σ –cyclopentadienyl complexes.
II- Fluorocarbon alkyl and aryl complexes, M-Rf .and the acyl
complexes M- CORf
III- Acetylide or alkynyl complexes M-C ≡ CR.
I- ( 1 ) Hydrocarbon alkyl and aryl complexes
It is convenient to classify these complexes according to the other
ligands attached to the metal.

90
However, only those MRh complexes in which all or most of the
other ligands are the same sort and which occur in substantial
numbers are classified by that ligand, viz.
(a) M-Rh complexes with tertiary phosphines and related ligands.
(b) -cyclopentadienyl carbonyl complexes.
(c) Bis--cyclopentadienyl complexes.
(d) carbonyl complexes.
Other complexes are more convenient classified by the metal, viz.
(e) Pure alkyl and aryl complexes and alkylhalide complexes of Ti,
V, Nb, Ta and Mn.
(f) Alkyl and aryl complexes of Cr
(g) Alkyl and aryl complexes of Co(III)
(h) Alkyl complexes of Pt(IV)
(i) Alkyls and aryls of Cu, Ag and Au

General preparative methods.

The successful preparation of metal-Rh complexes usually requires
considerable attention to experimental detail, in particular, the
exclusion of oxygen is usually essential

(a) From Grignard reagents and organoalkali metal derivatives.

The normal procedure is to treat a metal halide complexes with
excess of Grignard reagent or organoalkali metal derivative in ether
solutions.

91
Typical reactions using organolithium compouds are shown below.

Grignard regents are not always alternative to the alkali metal

derivatives, organolithium reagents are frequently the more reactive
and more readily give fully alkylakd or arylated products. Some
examples of the use of Grignard reagents are :

92
 (b) From complex metal anions and organic halides.

Transition metal carbonyls and π-cyclopentadienyl metal carbonyls

form stable anions which are conveniently prepared by treatment of
the neutral complexes with sodium amalgam (2%) in THF.

93
 GENERAL CHEMICAL PROPERTIES
(a) Stability:
 The thermal and oxidative stability of transition metal-
alkyl and-aryl complexes varies widely and depends largely
on the other ligands attached to the metal.
 Metal--organo complexes usually are only thermally
stable when the organic ligand is non-labile, and usually the
other ligands attached to the metal are also non-labile.
 An important role of -bonding ligands is that they
stabilize the low oxidation states of transition metals and
thus allow them to attain the 18-electron environment.
(b) Cleavage reactions of the metal-carbon bond.
 The metal carbon bond is frequently cleaved by halogens
of the hydrogen halides.
 In both cases the metal halides are formed.
cis-(Et3P)2PtBr2 Br2 cis-(Et3P)2PtMe2 HCl cis-(Et3P)2Pt MeCl+CH4
Br2
Et2AuBr EtAuBr2
CCl4
 In a few cases, alkyl halides cause cleavage
cis-(Et3P)2Pt(CH2Ph)2 + 2 PhCH2I trans-(Et3P)2PtI2
(c) Insertion reactions:
M-Rh + X M-X-Rh
Where X = CO
MeMn(CO)5 + CO press MeCOMn(CO)4CO
“methyl manganese pentacarbonyl”
X = SO2

25 C
94
 -C5H5Fe(CO)2CH3+SO2 -C5H5Fe(CO)2SO2CH3
or X = olefins such as C2F4
3 R=CH
(CO)5Mn-R + CF2 = CF2 R = C H (CO)5 Mn CF2CF2R
6 5

III Transition Metal Acetylides and Alkynyls

 Those complexes which have a –C  CR system -
bonded to a metal atom are called acetylide or alkynyl
complexes.
 They may be classified according to the other ligands
which may be attached to the metal.
(i) “Pure” metal acetylides, e.g. (Cu-C CR), are
those complexes which contain only the metal and the
acetylide or alkynyl ligand.
(ii) Complex acetylides, e.g. K3[Fe(CCR)6], are
those where the acetylide or alkynyl ligand is part of a
transition metal complex anion.
(iii) Finally there is a variety of alkynyl complexes in
which other ligands are also attached to the metal
such as tertiary phosphines, and the -
cyclopentadienyl ligand.

A. “Pure” metal acetylides and alkynyls.

 The acetylides M2C2, where M = Cu, Ag or Au have
been long known and they are all explosive.
 Dry silver acetylide is particularly sensitive to shock.

95
 The compounds formed with alkynyl ligands, C  CR,
are generally more stable and, in a few cases form
discrete molecules.
 The complexes may be prepared by direct reaction
between the acetylene and a metal salt,

Aq./Acetome Soln., 15-20 C

(1) reduc. with SO2
AuCl3 aq. + KBr (PH C  CAu)x
(2) addn. of PhC CH

or, alkali metal salts can be used,

2CuI + 2 K C  CH 2 Cu C  CH + 2 KI 45 C Cu2C2 + HC CH

 The majority of the complexes are insoluble and the

alkynyl complexes are not hydrolysed by water. The
insolubility of these alkynyls suggests that they have a
polymeric nature.
 The complexes (MC  CR)x, where M = Cu, Ag or Au,
all react with ligands such as ammonia and the tertiary
phosphines.
 The ligands serve to depolymerize the complex by
replacement of one donor ligand by another,
e.g. PhC  CPh)n Et3P Et3 PAu C  C Ph Et2O Et3P AuBr + LiC  CPh
LiBr
PhC  CAuAsEt3 + p-MeC6H4NC Ph C  CAu CNC6H4Me + AsEt3

96
The Role of Organotransition Metal Complexes in some
Catalytic Reactions (homogeneous catalytic reactions)
 The use of transition-metal complexes for the conversion of
unsaturated hydrocarbons into polymers, alcohols, ketones,
carboxylic acids and the like, has generated an extensive patent.

 Stoichiometric Reactions:
 The transfer of atoms or groups of atoms from a metal atom
to a ligand and vice versa is one of the fundamental processes
involved in catalysis by metals.
 The metal atom or its ligand may be attacked by
electrophilic or nucleophilic reagents, but it may be difficult to
prove that an attacking reagent is bound to a metal before
transfer to a ligand occurs.
Coordinative Unsaturation:
 If two substances A and B are to react at a metal atom
contained in a complex in solution, then clearly there must be
vacant sites for their coordination.
 In 5- or 6-coordinated metal complexes, coordination sites
may be made available by dissociation of one or more ligands
either thermally or photochemically.
e.g. thermal dissociation
pph3 pph3
RhH(CO)(PPh3)3 RhH(CO)(PPh3)2 RhH(CO)(PPh3)
PR3
 Ni [P((o-toly)3]4 Ni[P(o-tolyl)3]3

97
 The iridium analog of the first complex, namely
IrH(CO)(PPh3, does not catalyze the reactions that the Rh
species does at 25 C, but will do so when dissociation is
induced either by heat or by ultraviolet irradiation.

Oxidative Addition Reactions: (discussed before)

 Only a few reactions are considered in detail
(A) Isomerisation of olefins
(B) Hydrogenation of olefins and acetylenes
(C) Hydroformylation and related carbonylation reactions.
(D) Dinerization, oligomerization and polymerization of olefins
and acetylenes.
(E) Misceellaneous reactions, e.g. the oxidation of ethylene to
acetaldehyde, some reactions catalysed by copper and nitrogen
fixation.

Applications of Organometallic Compounds As Catalysts

(Homogeneous and Heterogeneous Catalysts) :

Hydroformylation

Hydroformylation, also known as oxo synthesis or oxo

process, is an important industrial process for the production
of aldehydes from alkenes. This chemical reaction entails
the addition of a formyl group (CHO) and a hydrogen atom
to a carbon-carbon double bond. This process has undergone
continuous growth since its invention in the 1930s:
production capacity reached 6.6×106 tons in 1995. It is

98
 important because the resulting aldehydes are easily
converted into many secondary products. For example, the
resulting aldehydes are hydrogenated to alcohols that are
converted to detergents. Hydroformylation is also used in
specialty chemicals, relevant to the organic synthesis of
fragrances and natural products. The development of
hydroformylation, which originated within the German coal-
based industry, is considered one of the premier
achievements of 20th century industrial chemistry.

The process typically is accomplished by treatment of an

alkene with high pressures (between 10 to 100 atmospheres) of
carbon monoxide and hydrogen at temperatures between 40 and
200 °C. Transition metal catalysts are required.Catalysts

A generic rhodium catalyst, where PAr3 = triphenylphosphine or

its sulfonated analogue Tppts.
The original catalyst was HCo(CO)4, discovered by Otto
Roelen. Subsequent work demonstrated that the ligand
tributylphosphine (PBu3) improved the selectivity of the cobalt-

99
catalysed process. Since the 1970s, most hydroformylation
relies on catalysts based on rhodium. Subsequent research led to
the development of water-soluble catalysts that facilitate the
separation of the products from the catalyst.

Mechanism
The overall mechanism resembles that for homogeneous
hydrogenation with additional steps. The reaction begins with
the generation of coordinatively unsaturated metal hydrido
carbonyl complex such as HCo(CO)3 and HRh(CO)(PPh3)2.
Such species bind alkenes, and the resulting complex undergoes
a migratory insertion reaction to form an alkyl complex.

Selectivity
A key consideration of hydroformylation is the "normal" vs.
"iso" selectivity. For example, the hydroformylation of
propylene can afford two isomeric products, butyraldehyde or
isobutyraldehyde:
H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO ("normal")
vs.
H2 + CO + CH3CH=CH2 → (CH3)2CHCHO ("iso")
These isomers result from the differing ways of inserting the
alkene into the M-H bond. Of course, both products are not
equally desirable. Much research was dedicated to the quest for
catalyst that favored the normal isomer.

100
Steric effects
When the hydrogen is transferred to the carbon bearing the most
hydrogen atoms (Markovnikov addition) the resulting alkyl
group has a larger steric bulk close to the ligands on the cobalt.
If the ligands on the cobalt are bulky (such as tributyl
phosphine), then this steric effect is greater. Hence the mixed
carbonyl/phosphine complexes offer a greater selectivity
towards the straight chain products.

Electronic effects
In addition the more electron rich the hydride complex is, the
less proton like the hydride is, thus as a result the electronic
effects which favour the markovnikov addition to an alkene are
less able to direct the hydride to the carbon atom bearing the
most hydrogens already. Thus as a result as the metal centre
becomes more electron rich the catylst becomes more selective
for the straight chain compounds.

101
Acetyl formation
Cobalt carbonyl and rhodium complexes catalyse the
hydroformylation of formaldehyde and ethylene oxide to give 2-
hydroxyacetaldehyde and 3-hydroxypropanaldehyde, which can
then be hydrogenated to ethylene glycol and 1,3-propanediol,
respectively. The
reactions work best when the solvent is basic (such as pyridine).
After the alkyl formation a second migatory insertion converts
the alkyl into an acetyl ligand (this is when the alkyl carbon
forms a bond with the carbon of a carbonyl ligand). The vacant
site on the metal is filled by two hydrogens (from the oxidative
insertion of a hydrogen molecule. One of these hydrides then
takes part in a reductive elimination to form the molecule of the
aldehyde .

Monsanto process
Introduction
The Monsanto process is an important method for the
manufacture of acetic acid by catalytic carbonylation of
methanol. This process operates at a pressure of 30–60 atm and
a temperature of 150–200 °C and gives a selectivity greater than
99%. It was developed 1960 by German BASF and improved by
[1]
Monsanto in 1966, who introduced a new catalyst system.
The Monsanto process has largely been supplanted by the
Cativa process, a similar iridium-based process developed by

102
BP Chemicals Ltd which is more economical and
environmentally friendly.
The Monsanto acetic acid process is the major commercial
production method for acetic acid. Methanol, which can be
generated from synthesis gas ("syn gas", a CO/H2 mixture), is
reacted with carbon monoxide in the presence of a catalyst to
afford acetic acid. In essence, the reaction can be thought of as
the insertion of carbon monoxide into the C-O bond of
methanol, i.e. the carbonylation of methanol.

This process has largely replaced an earlier synthetic method

called the Wacker process. Over 1,000,000 tons of acetic acid
are produced every year using the Monsanto process. The
reaction is highly selective, goes in high yield, and is extremely
fast.
The catalysts
The catalyst system has two components, iodide and rhodium.
Almost any source of Rh and I- will work in this reaction as they
will be converted to the actual catalyst, [Rh(CO)2I2]- under the
reaction conditions.
The role of iodide is simply to promote the conversion of
methanol to methyl iodide, the species which then undergoes
reaction with the Rh metal catalyst:

103
The catalytic cycle
Once methyl iodide has been generated, the catalytic cycle
begins with the oxidative addition of methyl iodide to
[Rh(CO)2I2]-. Coordination and insertion of carbon monoxide
leads an intermediate 18-electron acyl complex which can then
undergo reductive elimination to yield acetyl iodide and
regenerate our catalyst:

Notice that there are two catalytic cycles going in this reaction.
The blue one involves the metal and the red one involves iodide.
The acetyl iodide produced in the lower cycle is then
hydrolyzed in the upper one to give acetic acid. This hydrolysis

104
produces HI which can then convert more methanol to iodide
and continue the cycle:

In summary, the system is catalytic in both Rh and I-.

Limitations/Drawbacks
While the process is terrific, there are two major concerns:
1-Rhodium is an expensive starting material. 1 mole of
RhCl3.3H2O costs ~ $30,000!
2-I2 is cheap (about $20 per mole), but is extremely corrosive.
Other halogens or halogen substitutes do not work nearly as
well.

105
Catalytic cycle

rhodium centre on the carbon of methyl iodide. The catalytically

active species is the anion cis-[Rh(CO)2I2]− (1). The catalytic
cycle has been shown to involve six steps, two of which do not
involve rhodium: conversion of methanol to methyl iodide and
the hydrolysis of the acetyl iodide to acetic acid. The first
organometallic step is the oxidative addition of methyl iodide to
cis-[Rh(CO)2I2]− to form the hexacoordinate species
[(CH3)Rh(CO)2I3]− (2). This anion rapidly transforms, via the
migration of a methyl group to the carbonyl ligand, affording
the pentacoordinate acetyl complex [(CH3CO)Rh(CO)I3]− (3).

106
This five-coordinate complex then reacts with carbon monoxide
to form the six coordinate dicarbonyl complex (4) which
decomposes by reductive elimination to form acetyl iodide
(CH3COI) and regenerate the active form of the catalyst. Acetyl
iodide is then hydrolyzed to acetic acid.[2]
The reaction has been shown to be first-order with respect to
methyl iodide and the catalyst (1). Hence the rate-determining
step of the catalytic cycle has been proposed to be the oxidative
addition of methyl iodide to the catalyst (1). It is believed that
this occurs via the nucleophilic attack by the

Wacker process for synthesis of acetaldehyde .

The Wacker process or the Hoechst –Wacker process ( named
after the chemical companies of the same name) originally
referred to the oxidation of ethylene to acetaldehyde by oxygen
in water in the presence of a tetrachloropaladate catalyst.
The same basic reaction is currently used to produce aldehydes
and ketones from a number of alkenes with Monsanto process
for producing acetic acid. This chemical reaction a ferman
invention, was the first organometallic and organopalladium
reaction applied on an industrial scale . The Wacker process is
similar to hydroformylation , whch is also an industrial process
and also leads to aldehyde compounds. The differences are that
hydroformylation promotes chain extension , and uses a
rhodium-based catalyst system . The Wacker process is an
example of homogenous catalysis.

107
 The palladium complex with ethylene is reminiscent Zeise`s
salt , K[ PtCl3 (C2H4)] Which is a heterogeneous catalyst .
Wacker process, an industrial process for the manufacture of
ethanol by oxidizing ethane . For example , bubbling ethylene
and oxygen when treated by acidified water solution of palladium
and cupric chlorides yield acetaldehyde , reaction is catalyzes by
PdCl2- CuCl2 During the reaction palladium forms a complex with
ethylene , is reduced to Pd(0) , and then reoxidized by Cu(II) .
The process is run in one vessel at 50- 130 oC and at pressures of
3-10 atm. Regeneration of cupric chloride occurs in a separate
oxidizer. The favorable economics of the process is due to the
abundance of ethylene . Oxidation of propylene to acetone is
accomplished at 110-120oC with 10-14 atm.
History
The development of the chemical process now known as the
Wacker process began in 1956 at Wacker Chemie .At the time ,
many simple aliphatic compounds were produced
From acetylene ( as calcium carbide) but the construction of a
new oil refinery in Cologne by Esso close to a Wacker site,
combined with the realization that ethylene would be a cheaper
raw-material prompted Wacker to investigate its potential uses.
As a part of the ensuring research effort , a reaction of ethylene
and oxygen over palladium on carbon in a quest for ethylene
oxide unexpectedly gave evidence for the formation of
acetaldehyde ( simply based on smell) . More research into this
ethylene to acetaldehyde conversion resulted in 1957 in a gas-

108
phase reaction patent using a heterogeneous catalyst . In the
meanwhile Hoechest AG joined the race and after a patent filing
forced Wacker into a partnership called Aldehyde GmbH . The
heterogeneous process ultimately failed due to Catalyst
inactivation and was replaced by the water-based omogeneous
system for which A pilot plant was operationally in 1958.
Problems with the aggressive catalyst solution were solved by
adopting titanium ( newly available for industrial use ) as
construction material for reactors and pumps. Production plants
went into operation in 1960.
Reaction mechanism
The reaction mechanism for the industrial Wacker process
(olefin oxidation via palladium(II) chloride) has received
significant attention for several decades, and parts of it are still a
contentious subject. A modern formulation is described below:

The

109
catalytic cycle can also be described as follows:
[PdCl4]2 − + C2H4 + H2O → CH3CHO + Pd + 2 HCl + 2 Cl−
Pd + 2 CuCl2 + 2 Cl − → [PdCl4]2− + 2 CuCl
2 CuCl + ½ O2 + 2 HCl → 2 CuCl2 + H2O
Note that all catalysts are regenerated and only the alkene and
oxygen are consumed. Without copper(II) chloride as an
oxidizing agent Pd(0) metal (resulting from reductive
elimination of Pd(II) in the final step) would precipitate out and
the reaction would come to a halt (the stoichiometric reaction
without catalyst regeneration was discovered in 1894). Air, pure
oxygen, or a number of other oxidizers can then oxidise the
resultant CuCl back to CuCl2, allowing the cycle to repeat.

Hydrogenation
Hydrogenation, to treat with hydrogen, also a form of chemical
reduction, is a chemical reaction between molecular hydrogen
(H2) and another compound or element, usually in the presence
of a catalyst. The process is commonly employed to reduce or
saturate organic compounds. Hydrogenation typically
constitutes the addition of pairs of hydrogen atoms to a
molecule, generally an alkene. Catalysts are required for the
reaction to be usable; non-catalytic hydrogenation takes place

110
only at very high temperatures. Hydrogen adds to double and
triple bonds in hydrocarbons.
Because of the importance of hydrogen, many related reactions
have been developed for its use. Most hydrogenations use
gaseous hydrogen (H2), but some involve the alternative sources
of hydrogen, not H2: these processes are called transfer
hydrogenations. The reverse reaction, removal of hydrogen
from a molecule, is called dehydrogenation. A reaction where
bonds are broken while hydrogen is added is called
hydrogenolysis, a reaction that may occur to carbon-carbon and
carbon-heteroatom (oxygen, nitrogen or halogen) bonds.
Hydrogenation differs from protonation or hydride addition: in
hydrogenation, the products have the same charge as the
reactants.
Process
Hydrogenation has three components, the unsaturated substrate,
the hydrogen (or hydrogen source) and, invariably, a catalyst.
The reaction is carried out at different temperatures and
pressures depending upon the substrate and the activity of the
catalyst.
Substrate
The addition of H2 to an alkene affords an alkane in the
protypical reaction:
RCH=CH2 + H2 → RCH2CH3 (R = alkyl, aryl)

111
Hydrogenation is sensitive to steric hindrance explaining the
selectivity for reaction with the exocyclic double bond but not
the internal double bond.
An important characteristic of alkene and alkyne
hydrogenations, both the homogeneously and heterogeneously
catalyzed versions, is that hydrogen addition occurs with "syn
addition", with hydrogen entering from the least hindered side.
Typical substrates are listed in the table
Substrates for and products of hydrogenation
alkene, R2C=CR'2 alkane, R2CHCHR'2
alkyne, RCCR alkene, cis-RHC=CHR'

aldehyde, RCHO primary alcohol, RCH2OH

Catalysts
With rare exceptions, no reaction below 480 °C (750 K or 900
°F) occurs between H2 and organic compounds in the absence of
metal catalysts. The catalyst binds both the H2 and the
unsaturated substrate and facilitates their union. Platinum group
metals, particularly platinum, palladium, rhodium, and
ruthenium, form highly active catalysts, which operate at lower
temperatures and lower pressures of H2.
Two broad families of catalysts are known - homogeneous
catalysts and heterogeneous catalysts. Homogeneous catalysts
dissolve in the solvent that contains the unsaturated substrate.
Heterogeneous catalysts are solids that are suspended in the

112
same solvent with the substrate or are treated with gaseous
substrate.
Homogeneous catalysts
Illustrative homogeneous catalysts include the rhodium-based
compound known as Wilkinson's catalyst and the iridium-based
Crabtree's catalyst. An example is the hydrogenation of
carvone:

Hydrogenation is sensitive to steric hindrance explaining the

selectivity for reaction with the exocyclic double bond but not
the internal double bond.
The activity and selectivity of homogeneous catalysts is
adjusted by changing the ligands. For prochiral substrates, the
selectivity of the catalyst can be adjusted such that one
enantiomeric product is favored. Asymmetric hydrogenation is
also possible via heterogeneous catalysis on a metal that is
modified by a chiral ligand.
In many homogeneous hydrogenation processes, the metal binds
to both components to give an intermediate alkene-metal(H)2
complex. The general sequence of reactions is assumed to be as
follows or a related sequence of steps:

113
 binding of the hydrogen to give a dihydride complex
("oxidative addition"): LnM + H2 → LnMH2
 binding of alkene:
LnM(η2H2) + CH2=CHR → Ln-1MH2(CH2=CHR) + L
 transfer of one hydrogen atom from the metal to carbon
(migratory insertion)
Ln-1MH2(CH2=CHR) → Ln-1M(H)(CH2-CH2R)
 transfer of the second hydrogen atom from the metal to
the alkyl group with simultaneous dissociation of the alkane
("reductive elimination")
Ln-1M(H)(CH2-CH2R) → Ln-1M + CH3-CH2R
Preceding the oxidative addition of H2 is the formation of a
dihydrogen complex

Heterogeneous catalysts
Heterogeneous catalysts for hydrogenation are more common
industrially. As in homogeneous catalysts, the activity is
adjusted through changes in the environment around the metal,
i.e. the coordination sphere. Different faces of a crystalline
heterogeneous catalyst display distinct activities, for example.
Similarly, heterogeneous catalysts are affected by their supports,
i.e. the material upon with the heterogeneous catalyst is bound.
On solids, the accepted mechanism today is called the Horiuti-
Polanyi mechanism.
1. Binding of the unsaturated bond, and hydrogen
dissociation into atomic hydrogen onto the catalyst

114
2. Addition of one atom of hydrogen; this step is reversible
3. Addition of the second atom; effectively irreversible
under hydrogenating conditions.
For aromatic substrates, the first bond is hardest to hydrogenate
because of the free energy penalty for breaking the aromatic
system. The product of this is a cyclohexadiene, which is
extremely active and cannot be isolated; in conditions reducing
enough to break the aromatization, it is immediately reduced to
a cyclohexene. The cyclohexene is ordinarily reduced
immediately to a fully saturated cyclohexane, but special
modifications to the catalysts (such as the use of the anti-solvent
water on ruthenium) can preserve some of the cyclohexene, if
that is a desired product.

Hydrogen sources
For hydrogenation, the obvious source of hydrogen is H2 gas
itself, which is typically available commercially within the
storage medium of a pressurized cylinder. The hydrogenation
process often uses greater than 1 atmosphere of H2, usually
conveyed from the cylinders and sometimes augmented by
"booster pumps". Gaseous hydrogen is produced industrially
from hydrocarbons by the process known as steam reforming.
Hydrogen may, in specialised applications, also be extracted
("transferred") from "hydrogen-donors" in place of H2 gas.
Hydrogen donors, which often serve as solvents include
hydrazine, dihydronaphthalene, dihydroanthracene, isopropanol,

115
and formic acid. In organic synthesis, transfer hydrogenation is
useful for the reduction of polar unsaturated substrates, such as
ketones, aldehydes, and imines.
Thermodynamics and mechanism
Hydrogenation is a strongly exothermic reaction. In the
hydrogenation of vegetable oils and fatty acids, for example, the
heat released is about 25 kcal per mole (105 kJ/mol), sufficient
to raise the temperature of the oil by 1.6-1.7 °C per iodine
number drop. The mechanism of metal-catalyzed hydrogenation
of alkenes and alkynes has been extensively studied.[11] First of
all isotope labeling using deuterium confirms the regiochemistry
of the addition:
RCH=CH2 + D2 → RCHDCH2D
Wilkinson's catalyst :

Wilkinson's catalyst is the common name for

chlorotris(triphenylphosphine)rhodium(I), a coordination
compound with the formula RhCl(PPh3)3 (Ph = phenyl). It is
named after the late organometallic chemist and 1973 Nobel
Laureate, Sir Geoffrey Wilkinson who popularized its use.

116
Structure and basic properties
The compound is a square planar, 16-electron complex. It is
usually obtained in the form of a red-violet crystalline solid
from the reaction of rhodium(III) chloride with excess
triphenylphosphine. The synthesis is conducted in refluxing
ethanol. Triphenylphosphine serves as the reducing agent
yielding triphenylphosphine oxide.
RhCl3(H2O)3+4 PPh3 → RhCl(PPh3)3 + O=PPh3 +2HCl + 2 H2O
Catalytic applications
Wilkinson's catalyst catalyzes the hydrogenation of alkenes.[2][3]
The mechanism of this reaction involves the initial dissociation
of one or two triphenylphosphine ligands to give 14- or 12-
electron complexes, respectively, followed by oxidative
addition of H2 to the metal. Subsequent π-complexation of
alkene, intramolecular hydride transfer (olefin insertion), and
reductive elimination results in extrusion of the alkane product,
e.g.:

117
Other reactions of RhCl(PPh3)3
RhCl(PPh3)3 reacts with CO to give trans-RhCl(CO)(PPh3)2,
which is structurally analogous to Vaska's complex (but much
less reactive). The same complex arises from the
decarbonylation of aldehydes:
RhCl(PPh3)3 + RCHO → RhCl(CO)(PPh3)2 + RH + PPh3
Upon stirring in benzene solution, RhCl(PPh3)3 converts to the
poorly soluble red-colored species Rh2Cl2(PPh3)4. This
conversion further demonstrates the liability of the
triphenylphosphine ligands.

118
Catalytic cycle for hydrogenation with Wilkinson's catalyst.

119
Coordination (Ziegler-Natta) Polymerization
Ziegler-Natta polymerization is a method of vinyl
polymerization. It's important because it allows one to make
polymers of specific tacticity. It was discovered by two
scientists, and I think we can all figure out what their names
were. Ziegler-Natta is especially useful, because it can make
polymers that can't be made any other way, such as linear
unbranched polyethylene and isotactic polypropylene. Free
radical vinyl polymerization can only give branched
polyethylene, and propylene won't polymerize at all by free
radical polymerization. So this is a pretty important
polymerization reaction, this Ziegler-Natta stuff.
We know that it involves transition metal catalyst, like TiCl3.
We also know that co-catalysts are involved, and these are
usually based on group III metals like aluminum. Most of the
time our catalyst/co-catalyst pair are TiCl3 and Al(C2H5)2Cl, or
TiCl4 with Al(C2H5)3.

120
Early work:
Insertion of aluminum alkyls into olefins was studied by
Ziegler:

Important discovery: R3Al + Lewis acids:

Another important discovery: tacticity control:

Results:
 Nobel Prize in Chemistry for Zeigler and Natta (1963)
 Multibillion $ industry

121
Overall Scheme of Coordination Polymerization

 Limited to ethylene and other a-olefins like propylene.

(Actually, it is the only good way to polymerize these
monomers.)
 Produces linear polymer, with very few branches (e.g.,
high density polyethylene, HDPE).
 Capable of producing homo-tactic polymers.
 Most commercial initiators are insoluble complexes or
supported on insoluble carriers.
 Very complex mechanism, still poorly understood for the
heterogeneous systems.
 Termination is almost exclusively by chain transfer.
 Modern "high mileage" initiators produce up to 1000's of
kg per g initiator.
 Initiators are often called "catalysts" even though they
are consumed by the process. Many chains are started per
molecule of initiator.
Mechanism of Coordination Polymerization
The mechanism is poorly understood because it takes place on
the surface of an insoluble particle, a difficult situation to probe
experimentally. The mechanism shown below is one of several
models proposed to at least partially explain the action of the

122
Ziegler-Natta systems, but it is only an approximation of the
more complex process that actually occurs.

123
Limitations
Ziegler-Natta polymerization is a great way to make polymers
from hydrocarbon monomers like ethylene and propylene. But it
doesn't work of for some other kinds of monomers. For
example, we can't make poly(vinyl chloride) by Ziegler-Natta
polymerization. When the catalyst and cocatalyst come together
to form the initiating complex, radicals are produced during
intermediate steps of the reaction. These can initiate free radical
polymerization of the vinyl chloride monomer. Acrylates are
out, too, because Ziegler-Natta catalysts often initiate anionic
vinyl polymerization in those monomers

Carbonylation Reactions. (Hydroformylation)

 defintion:
The hydroformylation reaction is the addition of H2 and CO (or
formally of H and the formyl group, HCO) to an alkene, usually
l-alkene, to form an aldehyde which may be further reduced to
the alcohol:
RCH = CH2 + H2 + CO RCH2CH2CHO H2
RCH2CH2CH2OH
Originally cobalt compounds were used as catalysts at
temperatures of ca. 150 and > 200 atom pressure, and some
3000,000 tons a year of alcohols, usually C7-C9, are produced in

124
this way. The process ordinarily gives both straight-and
branched chain products in the ratio ca 3:1.
 The cobalt system is difficult to study and further
information on the catalyst cycle is provided by use of
RhH(CO)(PPh3)3, RhH(CO)2(PPh3)2
 This complex is catalytically active even at 25 C and 1
atom pressure and in contrast to the cobalt system, produces
only aldehyde.
 On use of high concentrations of PPh3, high yields of linear
aldehyde can be obtained with little or no loss of alkene as
alkane (which is a disadvantage of the cobalt system).
 The reaction cycle is shown below
 The intial step is associative attack of the alkene on the
species
Rh H(CO)2 (PPh3)2, [A]

R CH2CH2R
H H
Ph3P R Ph3P
fast Ph3P fast Rh
Rh CO Rh CO
Ph3P Ph3P Ph3P [B]
CO
CO CO CO

H OC CH2CH2R
Ph3P H Ph3P
Rh + H2
Rh
Ph3P slow Ph3P
COCH2CH2R
CO CO [C]
[D]
CO OC CH2CH2R
Ph3P
Rh CO
125 Ph3P
CO [F]
Which leads to the alkyl compex [B],
 The latter then undergoes CO insertion to form the acyl
derivative [C]. which subsequently adds hydrogen oxidatively
to give the dihydridoacyl complex [D].
 The last of these steps which is the only one in the cycle that
involves a change in oxidation state of the metal, is probably
rate-determining.
 The final steps are another H transfer to the carbon atom of
the acyl group in [D], followed by loss of aldehyde and
generation of the 4-coordinate species [E]

H H
PPh3 Ph3P
RCHO pph3
[D] Rh Rh PPh3
fast Ph3P Ph3P
CO CO
[E]
Another important commercial process is the carbonylation of
methanol to give acetic acid.
 Cobalt was used originally but high temperatures and
pressures were required, with rhodium much milder condition
can be used. The key to the reaction is the presence of iodide,
which react to give methyl iodide.
CH3 OH + HI CH3I + H2O

126
The MeI then oxidatively adds:
CH3
LnRhI + CH3I LnRh -I
Which is followed by CO insertion and hydrolysis:

CH3

CH3 CO
Ln-Rh -I CO LnRh-I HOH LnRhI + HI + CH3COOH

Dinitrogen, Dioxygen and Carbene Transition Metal

Complexes:
Many of the reaction to be discussed in this chapter do not
involve carbon-T.M bonds, but they are nonetheless of
considerable concern to organometallic chemists because of
their potential applications.
Dinitrogen Complexes:
 A wide variety of nitrogen transition metal complexe, are
known.
 The first isolable nitrogen complexes were made by reaction
of T.M. complexes with hydrazine.
 The metal complex is reduced to a lower oxidation state and
the hydrazine is oxidized to nitrogen presumably within the
coordinating sphere of the metal.
 The following examples are typical syntheses.
RuCl3 + NH2NH2.H2O [Ru(NH3)5N2]Cl2
(NH4)2 OsCl6 + NH2NH2.H2O [Os(NH3)N2]Cl2
 In these and other mononuclear nitrogen complexes
coordination occurs with an unshared pair of electrons on one of

127
the nitrogen and not by complexing with the (N N) triple
nitrogen-nitrogen bond.
 Nitrogen is a moderate -acceptor and weak -donor ligand.
 The oxidation of a coordinated hydrazine group by an
external oxidant also is possible
CO CO
2+ 40 C Mn N2 + 4H2O
Mn NH2 NH2 + Cu

CO CO
 In other reactions hydrazine may form mononitrogen
complexes (nitrides) as in its reaction with dirhenium heptoxide
and triphenylphosphine
Re2O7 + PP3 + NH2NH2.2HCl N  ReCl2(PPh3)2
N-substituted nitride are obtained with symmetrically
disubstituted hydrazines
CH3NH NHCH3.2HCl + ORe Cl3 (PPh3)2 PP3 CH3N
ReCl3(PPh3)2 + CH3NH3 Cl- + OPPh3.
 An indirect rout to dinitrogen complexes is the reaction of
coordinated ammonia with NO.
3+ 2+
Ru(NH3)6 + NO + OH- Ru(NH3)5N2
Most T.M. have now yielded complexes with molecular
nitrogen of one kind or another by the reduction procedure. The
following are a few more examples.
MoCl4(PMe2Ph)2 + NaHgx + 2 N2
N2 + Niacac2 + i-Bu3Al + PEt3 H NiN2(PEt3)2
Fe Cl2. 2H2O + NaBH4 + N2 + PPh2Et H2FeN2(PPh2Et)3

128
2- Dioxygen Complexes:
 The oxidation of organic compounds with molecular oxygen
and transition metal catalysts is of considerable economic
importance.
Preparation:
 most of the known complexes with metal groups attached to
both ends of the oxygen molecule are cobalt complexes.
 Many Co(II) complexes react with O2 to form binuclear
Co(III) peroxy complexes
e.g.
2 K3Co(CN)5 + O2 K6[(CN)5-Co-O-O-Co(CN)5]
 many complexes with metal oxygen atoms of an O2 group
bonded to the same metal are now known. These are generally
prepared by reactions of low-valent coordinately unsaturated or
easily dissociated saturated complexes with oxygen.
e.g.

Ph3P O
Pt(PPh3)3 + O2 pt + pph3
Ph3P O

t
Bu NC O
Ni(CNBu-t)4O2 Ni + 2t-BuNC
t
Bu NC O

129
Reactions:
 The T.M. dioxygen complexes undergo reaction with a
variety of compdounds.
 Addition reaction occur with CO2, ketones, and SO2 to give
cyclic peroxy complexes.

Ph3P O Ph3P O
O
pt + CO2 pt
C=O
Ph3P O Ph3P O

Ph3P O Ph3P O
O
pt + CH3COCH3 pt
C (CH3)2
Ph3P O Ph3P O

 The SO2 adduct however, is unstable and it rearranges

rapidly to a complex with a bidentate sulfate ligand.
Ph3P
PPh3
I O I O O
Ir + SO2 Ir
S O
OC O OC O
PPh3 PPh3
PPh3
I O O
Ir S
O
OC O
PPh3

Ph3P O O Ph3P O Ph3P O C (CF2)

O O
pt CF3 CO CF3
+ CF3 C CF3 pt C (CF3)2 pt O
Ph3P O Ph3P O Ph3P O C (CF3)2
130
 The reaction with fluorinated ketones can give both five-and
six-membered ring products.

 CO reacts with peroxyplatinum complex to form a bidentate

carbonate complex.

P O P O
pt + CO pt C=O
P O P O

 It is also react with nitrogen dioxide to form a covalent

bisnitrate.

Ph3P O Ph3P ONO2

pt + 2NO2 pt
Ph3P O Ph3P ONO2

 Of particular interest to the chemical industry would be the

discovery of new way, to more selectively oxidize saturated and
aromatic hydrocarbon groups.

 Aromatic hydrocarbons have been oxidized to phenols in

resonable yields with combinations of T.M. catalysts and O2
with or without added reducing agents.
FeSO4
2C6H6 + O2 2C6H5OH
CuSO4

131
 2+
C6H6 + O2 + ascorbic acid Fe C6H5OH + dehydroascorbic
acid.
 The mechanism of these reaction have not been estabilshed.
Carbene Complexes:
Carbene are highly reactive species of the form RR/C:, with two
valence electrons that do not form bonds.
 The simplest example is methylene, H2C:
 Carbenes are intermediates in some organic reactions.
 The most common example of this, is formation of
dichlorocarbene by treatment of CHCl3 with a base
CHCl3 + OH- Cl- + H2O + :CCl2
 Carbene ligand are distinguishable from the two other
common divalent carbon ligands, CO, RNC, by the presence of
two groups attached to the divalent carbon.
 The substituents may be H2, organic groups, Hal, or various
O2, N2 or sulfur groups.
Methods of Preparation
 A general method of preparation was developed involving
reactions of metal carbonyls with strongly nucleophilic anions.

OLi +
Cr(CO)6 + LiN(Me)2 Et3O BF4
(CO)5 Cr C
NMe2

OC2 H5
W(CO)6 + C6H5Li (CO)5 Cr C
NMe2

OCH3
OLi H+ CH2N2 (OC) W C
(CO)5 W C 5
132 C6H5 Ph
  At leat seven other methods of preparation of carbene
complexes are now known.
 One method of preparation is reaction certain isocyanide
complexes with alcohols or amines.
NHC6H5
Cl C
Pd OCH3
Cl CNC6H5
CH3OH
Cl CN Ph
NHC6H5
Pd 4-CH3C6H4NH2 Cl C
Cl CN Ph Pd NHC6H4CH3
Cl CNC6H5

Reactions of carbene Complexes:

1- many of the isolable carbene complexes are capable of
transferring the carbene group to olefins to form cyclopropane
derivatives.
COOMe COOMe
C6H5 H COOMe
(CO)6 Cr C D H C6H5 H OCH3
+ C=C H + H
OCH3 H OCH3 C6H5
Me Me Me

Two isomeric
Methoxyphenyl carbene- pentacabonyl Cr(o)
 This reaction probably involve addition of the metalcarbene
group to the olefin followed by reductive elimination forming a
coordinatively unsaturated metal group and the cyclopropane

133
 H
PPh2 + PPh2 C
PhCH2NEt3Cl
(CO)6 W C = CH2 +: CCL2 (CO)4 W C H
PPh2 P.T.C. PPh2 C

Cl Cl
 The T.M.-carbene complexes also are reactive starting
matrials for preparing a variety of other organometallic and
inorganic complexes. Scheme (1).
 The carbene ligand in methoxymethylcarbenepentacarbonyl
Cr(O) is completely replaced when it is reacted with PHal3 or
pyridine.

NH2
(OC)5 Cr C
CH3
NH3 H
(CO)5 Cr N CH3
H2NOH
C
OCH3
(0) OCH3
(OC)5 Cr H2NN(CH3)2
C (CO)5 Cr N C CH3
qSH SQ
CH3 (CO)5 Cr
RSH (mercaptan) C
HON=CR2 CH3

(CO)5 Cr N = CR2
C6H11NC

OCH3
C CH3
(CO)5 Cr C
N C6H11

Scheme (1)

OMe
(CO)5 Cr C + PBr3 (CO)5 Cr PBr3
Me

OMe
(CO)5 Cr C + CH5H5N (CO)5 Cr NC5H5 + CH2 = CHOEt
Me

134
135
Fullerene chemistry

Fullerene chemistry is a field of organic chemistry devoted to

the chemical properties of fullerenes. Research in this field is
driven by the need to functionalize fullerenes and tune their
properties. For example fullerene is notoriously insoluble and
adding a suitable group can enhance solubility. By adding a
polymerizable group, a fullerene polymer can be obtained.
Functionalized fullerenes are divided into two classes:
exohedral with substituents outside the cage and endohedral
fullerenes with trapped molecules inside the cage.
Naming
Buckminsterfullerene (C60) was named after Richard
Buckminster Fuller, a noted architectural modeler who
popularized the geodesic dome. Since buckminsterfullerenes
have a shape similar to that sort of dome, the name was thought
appropriate. As the discovery of the fullerene family came after
buckminsterfullerene, the shortened name 'fullerene' is used to
refer to the family of fullerenes. The suffix “ene” indicates that

136
each C atom is covalently bonded to three others (instead of the
maximum of four), a situation that classically would correspond
to the existence of bonds involving two pairs of electrons
(“double bonds”).
Fullerenes are a form of carbon molecule that is neither graphite
nor diamond. They consist of a spherical, ellipsoid, or
cylindrical arrangement of dozens of carbon atoms. whereas
cylindrical fullerenes are known as "buckytubes" or
"nanotubes." Buckyballs and buckytubes have been the subject
of intense research, both for their unique chemistry and for their
technological applications, especially in materials science,
electronics, and nanotechnology.
Fullerenes occur only in small amounts naturally, but several
techniques for producing them in greater volumes have been
suggested. The modern technique uses a benzene flame to
produce fullerenes. Other techniques include the vaporization of
graphite rods and catalytic chemical vapor deposition from
ethanol vapor.
The fullerene family of carbon molecules possess a range of
unique properties. A fullerene nanotube has tensile strength
about 20 times that of high-strength steel alloys, and a density
half that of aluminum. Carbon nanotubes demonstrate
superconductive properties, and single nanotubes up to 4
centimeters in length have been synthesized. A range of
companies exists to develop nanotubes for commercial
applications, including computer memory, electronic wires, and

137
materials science. One day nanotubes could be used to create
futuristic computers not possible with conventional lithographic
techniques.
Nanotubes have been a central focus in the buzz surrounding the
emerging field of "nanotechnology." The association is
sometimes misleading; when physicist Richard Feynman
originally proposed building manufacturing systems that
assemble products on the molecular level ("molecular
nanotechnology"), he was talking about tiny, productive
machine systems, not the creation of exotic nano-scale materials
like fullerenes using macro-scale chemistry techniques. A tiny
factory built entirely out of fullerenes would qualify as
molecular nanotechnology, but fullerenes on their own do not.
This is a critical distinction often overlooked by some
academics, venture capitalists, and technologists who are fond
of using the word "nanotechnology" as a tool to attract funding
or attention.
Properties
For the past decade, the chemical and physical properties of
fullerenes have been a hot topic in the field of research and
development, and are likely to continue to be for a long time.
Popular Science has published articles about the possible uses
of fullerenes in armor. In April 2003, fullerenes were under
study for potential medicinal use: binding specific antibiotics to
the structure to target resistant bacteria and even target certain

138
cancer cells such as melanoma. Fullerenes used as light-
activated antimicrobial agents.
In the field of nanotechnology, heat resistance and
superconductivity are some of the more heavily studied
properties.
A common method used to produce fullerenes is to send a large
current between two nearby graphite electrodes in an inert
atmosphere. The resulting carbon plasma arc between the
electrodes cools into sooty residue from which many fullerenes
can be isolated.

Chemical properties of fullerenes

Fullerene or C60 is soccer-ball-shaped or Ih with 12 pentagons
and 20 hexagons. According to Euler's theorem these 12
pentagons are required for closure of the carbon network
consisting of n hexagons and C60 is the first stable fullerene
because it is the smallest possible to obey this rule. In this
structure none of the pentagons make contact with each other.
Both C60 and its relative C70 obey this so-called isolated
pentagon rule (IPR). The next homologue C84 has 24 IPR
isomers of which several are isolated and another 51,568 non-
IPR isomers. Non-IPR fullerenes have thus far only been
isolated as endohedral fullerenes such as Tb3NC84 with two
fused pentagons at the apex of an egg-shaped cage. or as
fullerenes with exohedral stabilization such as C50Cl10 and
reportedly C60H8.

139
Because of the molecule's spherical shape the carbon atoms are
highly pyramidalized, which has far-reaching consequences for
reactivity. It is estimated that strain energy constitutes 80% of
the heat of formation. The conjugated carbon atoms respond to
deviation from planarity by orbital rehybridization of the sp²
orbitals and pi orbitals to a sp2.27 orbital with a gain in p-
character. The p lobes extend further outside the surface than
they do into the interior of the sphere and this is one of the
reasons a fullerene is electronegative. The other reason is that
the empty low-lying pi* orbitals also have high s character

Solubility
Fullerenes are sparingly soluble in many solvents. Common
solvents for the fullerenes include aromatics, such as toluene,
and others like carbon disulfide. Solutions of pure
buckminsterfullerene have a deep purple color. Solutions of C70
are a reddish brown. The higher fullerenes C76 to C84 have a
variety of colors. C76 has two optical forms, while other higher
fullerenes have several structural isomers. Fullerenes are the
only known allotrope of carbon that can be dissolved in
common solvents at room temperature.
Some fullerene structures are not soluble because they have a
small band gap between the ground and excited states. These
include the small fullerenes C28, C36 and C50. The C72 structure
is also in this class, but the endohedral version with a trapped
lanthanide-group atom is soluble due to the interaction of the

140
metal atom and the electronic states of the fullerene.
Researchers had originally been puzzled by C72 being absent in
fullerene plasma-generated soot extract, but found in endohedral
samples. Small band gap fullerenes are highly reactive and bind
to other fullerenes or to soot particles.
Solvents that are able to dissolve buckminsterfullerene (C60) are
listed at left in order from highest solubility. The solubility
value given is the approximate saturated concentration.
Solubility of C60 in some solvents shows unusual behaviour due
to existence of solvate phases (analogues of crystallohydrates).
For example, solubility of C60 in benzene solution shows
maximum at about 313 K. Crystallization from benzene solution
at temperatures below maximum results in formation of triclinic
solid solvate with four benzene molecules C60·4C6H6 which is
rather unstable in air. Out of solution, this structure decomposes
into usual fcc C60 in few minutes' time. At temperatures above
solubility maximum the solvate is not stable even when
immersed in saturated solution and melts with formation of fcc
C60. Crystallization at temperatures above the solubility
maximum results in formation of pure fcc C60. Millimeter-sized
crystals of C60 and C70 can be grown from solution both for
solvates and for pure fullerenes. Fullerene chemistry involves
substituting metal atoms for one or more carbon atoms in the
molecule to produce compounds called
fullerides. Among these are conducting films of alkali metal-
doped fullerenes and superconductors (potassium-doped Tc

141
18°K;, rubidium-doped Tc 30°K;). Fullerenes also have been
used to produce tiny diamonds and thin diamond films.
Fullerene research is expected to lead to new materials,
lubricants, coatings, catalysts, electro-optical devices, and
medical applications.
In benzene solution, fullerene-60 is magenta and fullerene-70
red. Fullerene-60 forms translucent magenta face-centered cubic
(fcc) crystals that sublime. The ionization energy is 7.61 eV and
the electron affinity is 2.6–2.8 eV. The strongest absorption
bands lie at 213, 257, and 329 nanometers. Studies with nuclear
magnetic resonance spectroscopy yield a chemical shift of 142.7
parts per million; this result is commensurate with an aromatic
system.
Solid C60 exhibits interesting dynamic behavior in that at room
temperature the individual round molecules in the face-centered
cubic crystals are rotating isotropically (that is, freely) at around
108 Hz. At around 260 K (8.3°F) there is a phase transition to a
simple cubic (sc) lattice accompanied by an abrupt lattice
contraction. Rotation is no longer free, and the individual
molecules make rotational jumps between two favored (relative)
orientational configurations—in the lower-energy one a double
bond lies over a pentagon, and in the other it lies over a
hexagon. At 90 K (−300°F) the individual molecules stop
rotating altogether, freezing into an orientationally disordered
crystal involving a mix of the two configurations

142
Fullerene-60 behaves as a soft electrophile, a molecule that
readily accepts electrons during a primary reaction step. It can
readily accept three electrons and perhaps even more. The
molecule can be multiply hydrogenated, methylated,
ammonated, and fluorinated. It forms exohedral complexes in
which an atom (or group) is attached to the outside of the cage,
as well as endohedral complexes in which an atom is trapped
inside the cage.
The C60 molecule behaves as though it has only a single
resonance form—one in which the 30 double bonds are
localized in the bonds that interconnect the pentagons. This is a
key factor, as addition to these double bonds is the most
important reaction as far as the application of C60 in synthesis is
concerned.
On exposure of C60 to certain alkali and alkaline earth metals,
exohedrally doped crystalline materials are produced that
exhibit superconductivity at relatively high temperatures (10 to
33 K or −440 to −400°F). The C60 molecule has a triply
degenerate lowest unoccupied molecular orbital (LUMO),
which in the superconducting materials is half filled, containing
three electrons. Other ionic phases, such as MnC60 (n = 1, 2, 4,
6, where M is the intercalated metal atom), exist but are not
superconducting—they appear to be metallic or
semiconductor/insulators. See also Molecular orbital theory.
Perhaps the most important aspect of the fullerene discovery is
that the molecule forms spontaneously. This fact has important

143
implications for understanding the way in which extended
carbon materials form, and in particular the mechanism of
graphite growth and the synthesis of large polycyclic aromatic
molecules. It has become clear that as far as pure carbon
aggregates of around 60–1000 atoms are concerned, the most
stable species are closed-cage fullerenes.
Hydrated Fullerene (HyFn)
Hydrated fullerene C60HyFn is a stable, highly hydrophilic,
supra-molecular complex consisting of С60 fullerene molecule
enclosed into the first hydrated shell that contains 24 water
molecules: C60 (H2O)24. This hydrated shell is formed as a result
of donor-acceptor interaction between lone-electron pairs of
oxygen, water molecules and electron-acceptor centers on the
fullerene surface. Meanwhile, the water molecules which are
oriented close to the fullerene surface are interconnected by a
three-dimensional network of hydrogen bonds. The size of
C60HyFn is 1.6–1.8 nm. The maximal concentration of С60 in
the form of C60HyFn achieved by 2010 is 4 mg/mL.
Fullerene reactions
Fullerenes tend to react as electrophiles. An additional driving
force is relief of strain when double bonds become saturated.
Key in this type of reaction is the level of functionalization i.e.
monoaddition or multiple additions and in case of multiple
additions their topological relationships (new substituents
huddled together or evenly spaced).

144
Nucleophilic addition
Fullerenes react as electrophiles with a host of nucleophiles in
nucleophilic additions. The intermediary formed carbanion is
captured by another electrophile. Examples of nucleophiles are
Grignard reagents and organolithium reagents. For example the
reaction of C60 with methylmagnesium chloride stops
quantitatively at the penta-adduct with the methyl groups
centered around a cyclopentadienyl anion which is subsequently
protonated. Another nucleophilic reaction is the Bingel
reaction. Fullerene reacts with chlorobenzene and aluminium
chloride in a Friedel-Crafts alkylation type reaction. In this
hydroarylation the reaction product is the 1,2-addition adduct
(Ar-CC-H).
Hydrogenation
Fullerenes are easily hydrogenated by several methods.
Examples of hydrofullerenes are C60H18 and C60H36. However,
completely hydrogenated C60H60 is only hypothetical because of
large strain. Highly hydrogenated fullerenes are not stable,
prolonged hydrogenation of fullerenes by direct reaction with
hydrogen gas at high temperature conditions results in collapse
of cage structure with formation of polycyclic aromatic
hydrocarbons.
Oxidation
Although more difficult than reduction, oxidation of fullerene is
possible for instance with oxygen and osmium tetraoxide.

145
Hydroxylation
Fullerenes can be hydroxylated to fullerenols or fullerols.
Water solubility depends on the total number of hydroxyl
groups that can be attached. One method is fullerene reaction in
diluted sulfuric acid and potassium nitrate to C60(OH)15.
Another method is reaction in diluted sodium hydroxide
catalysed by TBAH adding 24 to 26 hydroxyl groups.
Hydroxylation has also been reported using solvent-free NaOH /
hydrogen peroxide. C60(OH)8 was prepared using a multistep
procedure starting from a mixed peroxide fullerene. The
maximum number of hydroxyl groups that can be attached
(hydrogen peroxide method) stands at 36-40.
Electrophilic addition
Fullerenes react in electrophilic additions as well. The reaction
with bromine can add up to 24 bromine atoms to the sphere. The
record holder for fluorine addition is C60F48. According to in
silico predictions the as yet elusive C60F60 may have some of the
fluorine atoms in endo positions (pointing inwards) and may
resemble a tube more than it does a sphere.
Fullerenes as ligands
Fullerene is a ligand in organometallic chemistry. The [6,6]
double bond is electron-deficient and usually forms metallic
bonds with η = 2 hapticity. Bonding modes such as η = 5 or η =
6 can be induced by modification of the coordination sphere.

146
 C60 fullerene reacts with tungsten hexacarbonyl W(CO)6 to the
(η²-C60)W(CO)5 complex in a hexane solution in direct sunlight.
Multistep fullerene synthesis
Although the procedure for the synthesis of the C60 fullerene is
well established (generation of a large current between two
nearby graphite electrodes in an inert atmosphere) a 2002 study
described an organic synthesis of the compound starting from
simple organic compounds.

In the final step a large polycyclic aromatic hydrocarbon

consisting of 13 hexagons and three pentagons is submitted to
flash vacuum pyrolysis at 1100°C and 0.01 Torr. The three
carbon chlorine bonds serve as free radical incubators and the
ball is stitched up in a no-doubt complex series of radical
reactions. The chemical yield is low: 0.1 to 1%. A small
percentage of fullerenes is formed in any process which
involves burning of hydrocarbons, e.g. in candle burning. The

147
yield through a combustion method is often above 1%. The
method proposed above does not provide any advantage for
synthesis of fullerenes compared to the usual combustion
method, and therefore, the organic synthesis of fullerenes
remains a challenge for chemistry.
Nanotube chemistry
Carbon nanotubes, also part of the fullerene family, can be
described as graphene sheets rolled into a cylindrical tube.
Unlike the spherical fullerenes made up of hexagons and
pentagons, nanotubes only have hexagons present but in terms
of reactivity both systems have much in common. Due to
electrostatic forces nanotubes have a nasty tendency to cluster
together into bundles and many potential applications require an
exfoliation process. One way to do this is by chemical surface
modification.
A useful tool for the analysis of derivatised nanotubes is Raman
spectroscopy which shows a G-band (G for graphite) for the
native nanotubes at 1580 cm−1 and a D-band (D for defect) at
1280 cm−1 when the graphite lattice is disrupted with conversion
of sp² to sp³ hybridized carbon. The ratio of both peaks ID/IG is
taken as a measure of functionalization. Other tools are UV
spectroscopy where pristine nanotubes show distinct Van Hove
singularities where functionalized tubes do not, and simple TGA
analysis.

148
In one type of chemical modification, aniline is oxidized to a
diazonium intermediate. After expulsion of nitrogen, it forms a
covalent bond as an aryl radical:

Also known are protocols for Diels-Alder reactions, one assisted

by chromium hexacarbonyl and high pressure.
Nanotubes can also be alkylated with alkyl halides using lithium
or sodium metal and liquid ammonia (Birch reduction
conditions). The initial nanotube salt can function as an
polymerization initiator and can react with peroxides to form
alkoxy functionalized nanotubes
Types of fullerene
Since the discovery of fullerenes in 1985, structural variations
on fullerenes have evolved well beyond the individual clusters
themselves. Examples include:
 buckyball clusters: smallest member is C20 (unsaturated
version of dodecahedrane) and the most common is C60;
 nanotubes: hollow tubes of very small dimensions,
having single or multiple walls; potential applications in
electronics industry;

149
 megatubes: larger in diameter than nanotubes and
prepared with walls of different thickness; potentially used for
the transport of a variety of molecules of different sizes;
 polymers: chain, two-dimensional and three-dimensional
polymers are formed under high pressure high temperature
conditions
 nano"onions": spherical particles based on multiple
carbon layers surrounding a buckyball core; proposed for
lubricants;
 linked "ball-and-chain" dimers: two buckyballs linked
by a carbon chain,
 fullerene rings.

150
151
152
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