CYCLOPENTADIENE AND SUBSTITUTED CYCLOPENTADIENE

1.INTRODUCTION:

FEATURES:

Cyclopentadiene is a chemical compound with formula C5H6 .It is a colourless

liquid at room temperature and has a strong and unpleasant odour. It
spontaneously undergoes Diels-Alder reaction at room temperature to form
dimer dicyclopentadiene , this reaction is reversible at elevated temperature via
retro Diels-Alder reaction.

Molecular formula C5H6

Molar Mass 66.10 gm/mol
Appearance Colourless liquid (at room temp)
Density 0.81 gm/cm3 ,liquid
Solubility in water Insoluble
structure planar

STRUCTURE AND BONDING: Cp is planar cyclic molecule . The anionic

Cp molecule is an aromatic compound with 6π electrons . Due to stability of
anionic form of Cp is acidic with Pka = 16 which is unusual for
hydrocarbons.The anionic Cp reacts with many chemical species . The anion
acts as a weak nucleophile and it forms numerous cyclopentadiene complexes,
such as metallocenes. Cp ligands can form η1 , η3 and η5 complexes.

The MO scheme for C5H5 group

The five p orbitals on carbon give rise o five molecular orbitals for C5H5- group.
Important overlaps are ψ1 with dz2 , ψ2 and ψ3 with the dxz and dyz orbitals ψ4
and ψ5 do not interact very strongly with metal orbitals and Cp compound is
therefore not a good π acceptor .This and the anionic charge on Cp means that
Cp compound are generally basic , and presence of Cp encourages back
donations from metal to other \ligands present.

1
MO scheme:

1

2 3

4 5

Diels –Alder Reaction :

The Diels-Alder reaction is an organic chemical reaction (specifically, a

cycloaddition) between a conjugated diene and a substituted alkenes,
commonly termed the dienophile, to form a substituted cyclohexene system
Cyclopentadiene undergoes Diels –Alder reaction to form its dimer bridged

2
 2
This reaction is reversible and dicylopentadiene when heated over 1000C , it
produces cyclopentadiene via Retro Diels Alder reaction. This is also called
cracking of Cp2.

100 0C
2

PENTAMETHYLCYCLOPENTADIENE:
1,2,3,4,5-Pentamethylcyclopentadiene is a cyclic diolefin with the formula
C5Me5H, which is often denoted as Cp*, in contrast to Cp it does not dimerize.

The 1,2,3,4,5-pentamethylcyclopentadienyl ligand is a

complexing agent of great utility in main group,

transition metal, and f-element organomettallic

chemistry. The electron density of this ligand is

greater than compared to unsubstituted

cyclopentadienyl ligands, and generally imparts enhanced solubility and
crystallizability to a variety of metal complexes. As an ancilliary ligand, it
increases thermal stability in a number of metal hydrocarbyl systems. It is a
bulky ligand so its steric effects are also considerable and important, for
actinides it leads to coordinative unsaturation by restricting the number of
cyclopentadienyl groups that can bee bound to the metal ion.

Pentamethylcyclopentadiene is commercially available. It was first

prepared from tiglaldehyde via 2,3,4,5-tetramethylcyclopent-2-
enone. Alternatively 2-butenyllithium adds to ethylacetate followed by acid-
catalyzed dehydrocyclization:

MeCH=C(Li)Me + MeC(O)OEt → (MeCH=C(Me))2C(OLi)Me + LIOEt

(MeCH=C(Me))2C(OLi)Me + H+ → Cp*H + H2O + Li+

3
Preparation of Cp* :

A. Li
Br
Et2O
CH3CH=C + 2Li CH3CH=C + LiBr
CH3
CH3
OH
Li
Et2O H2O
CH3CH=C +
O
CH3

OH

C7H7SO3H
B.
-H2O

COMPARISON BETWEEN Cp AND Cp*:

Cp* is sterically more bulky and electron density on this is also greater than
Cp. Being more electron-rich, Cp* is a stronger donor and is less easily
removed from the metal. Consequently Cp* complexes exhibit increased
thermal stability.

Magnanocene and Rhenocenes demonstrate the effect of methyl substitution in

its properties. Whereas Cp2Mn cannot be reduced and monomeric Cp2Re has
only been detected in low-temperature matrices, both decamethylmagnanocene
and decamethylrhenocene form stable 18 VE anions.

4
 CYCLOPENTADIENYL COMPLEXES

The most important complexes of Cp is metallocenes,the metals bonded to two

cyclopentadienyls Cp in a pentahapto mode form the metallocenes. In many
other families of compounds , the metal is bonded to only one of Cp or
derivatives. Common examples of this category include ternary families
containing, besides the Cp type ligand, carbonyls, phosphines, nitrosyls ,
hydrides, oxo imido methyl, etc.

Some common examples :

Fe

Co(CO)2

OC CO
CO
Mo Mo
Fe
OC
CO CO Me3P PMe3
PMe3

O
N NO
Cr Cr
W
Cl Cl ON N
O
Cl Cl

5
 Re
Ta
O O H H
O H H

Ir

Ta N
Me Me
Me Me t-Bu

EXAMPLE OF COMLEXES OF Cp AND Cp*(above)

Cyclopentadiene is a good spectator ligand for a whole series of complexes

CpMLn, where we want chemistry to occur at MLn group or other ligand groups.
The one very important complex family based on Cp are metallocenes (e.g.-
ferrocene) , other classic families are [MCp(CO)3]2,M=Cr,Mo,or
W,[NiCp(CO)]2,mononuclear [VCp(CO)4],[MCp(CO)3],M=Mn,Tc, or Re,

[MCp(CO)2] ,M=Co,Rh,or Ir and tertiary nitrosyl complexes. With neutral Cp

complexes such as [VCp(CO)4],[MnCp(CO)3], it is possible to achieve
electrophilic substitution on the Cp ring similar to those known with ferrocene,
which allows to functionalize complexes in order to branch them on polymers,
electrodes, dendrimers and derivated silica for chromatography.

Although most of the time Cp forms a pentahapto complex, but there are
complexes of main group and transition metals containing one or several Cp
ligands that are monohapto coordinated.

6
 METALLOCENES
The first metallocenes discovered was ferrocene, the discovery of structure of
this compound by Wilkinson, Woodword and fischer in 1954 has been a starting
point for the boom of chemistry of π complexes. The prediction of sandwich
structure and aromaticity in this compound and further research by Fischer and
Wilkinson in the field of organomettallic chemistry resulted in both being
awarded Nobel prize in 1973. The family of metallocenes and
decamethylmetallocenes (MCp*2) now includes all transition and main group
metals. These have got multiple applications in the field of materials and
molecular engineering. Molecular fragments, modified electrodes for redox
catalysis (titration of glucose in blood), polymers and dendrirtic electrochemical
sensors for molecular recognition , antitumor drugs and paintings.

Metallocenes , in a broad sense , have the composition [MCp2] and are known
for all the transition metal and many main group and rare earth metals. Some
common examples of metallocenes are [FeCp2], [VCp2], [CrCp2], [NiCp2],
[NbCp2] .

STRUCTURE OF SOME METALLOCENES:

M Fe

A general metallocene structure ferrocene

Cr Co

7
 Chromrcene Cobaltocene

Ni Os

Nickelocene Osmocene

STRCTURE, BONDING AND PROPERTIES:

Ferrocene was the first metallocene which structure was deduced in 1954. The
structure was revealed by two groups in Cambridge (USA) and Munich
(Germany) based on experimental evidences:

Fischer: “Double –cone structure” based on-

*X-ray structural analysis

*Diamagnetism

*Chemical behaviour

Wilkinson, Woodward : “sandwich structure” based on-

*IR spectroscopy

*Diamagnetism

*Dipole moment = 0

8
Bonding in metallocenes:

If we put two Cp groups and one metal together , we obtain the MO diagram
for a metallocene (shown in figure). After this we have to look for symmetry of
Cp orbitals and how they interact with the metal orbitals.

MO orbital diagram and interactions in ferrocene:

In the given figure the interaction of Cp MO are described with that of iron in
the process of formation of ferrocene. Crystal field splitting pattern for Cp is
shown and molecular orbital formation in Cp and their interaction with orbitals
of Fe and filling of electrons in molecular orbitals is also shown.

(Formation of nodes in Cyclopentadiene)

9
 4p

4s 4
5

3d

2 

1

Group orbitals

Fe Fe

Bonding between metal atoms and Cp (using Fe as metal atom)

10
The d orbital occupation pattern for some first-row mettalocenes:

The splitting pattern for d orbitals is approximately same as for octahedral ML6.

Theoretical magnetic moment (µ=(n(n+1))0.5), no of unpaired electrons ,

experimental magnetic moment in, and colour of neutral metallocenes is also
given along with.

VCp2 CrCp2 MnCp2 FeCp2 CoCp2 NiCp2

NEV 15e 16e 17e 18e 19e 20e

e*1g
 bond
(xy, yz)

a'1g
z2  bond


e2g back-
2 2 bonding
x -y ,xy

unpaired
electrons 3 2 5 0 1 2

 B (theoretical) 3.87 2.83 5.92 0 1.73 2.93

 B (exper.) 3.84 3.20 5.81 0 1.76 2.86

Colour purple scarlet brown orange purple green

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Different methods for preparation of metallocenes:

A cyclopentadienyl compound was as early as 1901 by Thiele in the reaction:

benzene
C5H6 K K C5H5 ½ H2

Half a century later the discovery of this compound organomettallic compound

again become the matter of focus with discovery of ferrocene and its properties.

Two independent discoveries of ferrocene were reported –

*Miller, Tebboth, Tremaine (1951)

300 0C
2C5H6 + Fe (C5H5)2Fe + H2
Al, Mo oxides
The actual goal was synthesis of organic amine from dinitrogen and
cyclopentadiene in the presence of iron powder.

*Kealy, Pauson (1951)

3C5HMgBr FeCl3 Fe(C5H5)2 ½ C10H10 3MgBrCl

The actual aim of this synthesis was fulvalene (C 10H 8).

Binary Cyclopentadienyl metal complexes:

Preparation:

1. Metal salt + cyclopentadienyl reagent

Dicyclopentadiene is cracked first in a retro diels-alder reaction to give

monomeric C5H6. Cyclopentadiene is a weak acid (Pka=15) and can be
deprotonated by strong bases or by alkali metals. NaCp is most easily
commercially available reagent for the introduction of cyclopentadienyl
reagent.

180 0C Na
Cp2 2Cp 2NaC5H5 H2
MCl2 + 2NaC5H5 C5H5)2M ; M =V, Cr, Mn, Fe, Co
(Solvent=THF, DME, NH3)

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Ni(acac)2 2C5H5MgBr (C5H5)2Ni 2(acac)MgBr
NaC5H5 can behave as a ligand source as well as reducing agent also:
CrCl3 3NaC5H5 (C5H5)2Cr ½ C10H10 3NaCl

In many cases, treatment of NaC5H5 with metal (4d, 5d) salts does not give
Cp2M complexes, but rather Cp metal hydrides or complexes that bear σ-
bonded Cp rings.
NaCp NaCp
TaCl5 (5-Cp)2TaCl3 (5-Cp)2Ta(1-Cp)2
NaCp
ReCl5 ( 5-Cp)2ReH

2. Metal + Cyclopentadiene

M C5H6 MC5H5 1/2H2 M=Li, Na, K

500 0C
M + 2C5H6 (C5H5)2M + H2 M=Mg, Fe

3. Metal salt + Cyclopentadiene

In this process auxiliary base is needed if the basicity of the salt anion is in
sufficient to deprotonate cyclopentadiene:
H2O
Tl2SO4 + 2C5H6 + 2OH 2C5H5Tl + 2H2O + SO42
FeCl2 + 2C5H6 + 2Et2NH (C5H5)2Fe + 2[Et2NH2]ClIn
other cases a reducing agent is needed:
EtOH
RuCl3(H2O)x + 3C5H6 + 3/2 Zn (C5H5)2Ru + C5H8 + 3/2Zn2+

13
Some properties of metallocenes:

Complex Colour Melting Miscellaneous

0
Point ( C )
(C5H5)2Ti Green 200 Dimeric with two µ-h bridges and a
fulvalenediyl bridging ligand
(C5H5)2V purple 167 Very air sensitive
(C5H5)2Nb yellow Dimeric with η1: η5-C5H4 bridges
and terminal hydride ligands
(C5H5)2 Cr scarlet 17 3 Very air sensitive
(C5H5)2 Mo black Several dinuclear isomers with
fulvalenediyl or η1- η5 bridges and
terminal hydride ligands,
Diamagnetic
(C5H5)2W Yellow Same as above
Green
(C5H5)2Mn Brown 173 Air sensitive and readily hydrolyzed
;
At 158 0C converted into pink form
(C5H5)2Fe orange 173 Air stable ; can be oxidized to blue
green (C5H5)2Fe+
(C5H5)2Co Purple 174 Air-sensitive, oxidation gives the air
black stable, yellow cation (C5H5)2Co+
(C5H5)2Ni Green 173 Slow oxidation by air to the labile,
orange cation (C5H5)2Ni+

CHEMICAL PROPERTIES OF METALLOCENES:

1.REDOX PROPERTIES:-

A key property of metallocene is their ability to exist in the form of various

oxidation states with the sandwich structure and a variable no. Of d-electrons
(no.of valence electrons between 14 to 20), even if the stability decreases as the
NVE changes from 18. Each metallocene exists in various oxidation states
which is usually not the case for other families inorganic or organomettallic
compounds.

Monocationic metallocenes have been isolated and their stability is modest

when their NVE is different from 18, but dications are only isolable for
decamethylmetallocenes that are much more robust. The ferrocenium cations
are stable as various salts, but they are slightly air and light sensitive in solution.

14
these salts are very often used as mild monoelectronic oxidants, and the
reduction of ferrocenium salt can be easily achieved using an aqueous solution
of dithionite or TiCl3 or in organic solution using [FeCp*2] :

1. H2SO4 or HNO3
2. Aq. HPF6
Fe(Cp)2 [Fe(Cp)2]+ PF6-
3. Na2S2O3 or TiCl3

SELECTED REACTIONS OF METALLOCENES:

Owing to its high redox stability, ferrocene shows good organic reactivity. Thus
ferrocene , ruthenocene, and osmocene are susceptible to electrophilic
substitution. Ferrocene reacts 3*106 times faster than benzene:

E
E
E H
Fe Fe Fe
-HH

FRIEDAL-CRAFT ACYLATION:

The electrophile should not be an oxidizing agent, as substitution would then be

suppressed by oxidation to the ferricinium ion [FeCp2]+ .

15
 H H

H
Fe Fe Fe H

MANNICH REACTION (aminomethylation) :

CH2N(CH3)2

HCHO/HN(CH3)2
Fe Fe
HOAc

OXIDATION PROPERTIES OF METALLOCENE:

Ferrocene is easily oxidisable complex and its oxidation can be done chemically
as well as using oxidising agents (e.g. HNO3).
-e-
(C5H5)2Fe [(C5H5)2Fe]+
E0 = +0.40V, MeCN,
18 VE NBu4PF6 Vs SCE 17VE

the ferrocene/ferricinium couple has been accepted as internal standard in

organomettallic cyclovoltammetry.

Ruthenocene and osmocene can also be oxidised, but corresponding metallicillium

ions are not stble as monomers. Dimerization occurs or disproportionation
reaction occurs to yield Cp2M and [Cp2M]2+. In contrast permethylated complex
(C5Me5)2Ru forms a cation [(C5Me5)2Ru]+, which is stable at -30 0C.

16
The metallocenes of cobalt and nickel have the tendency to attain 18 VE
configurations:

Cobaltocene is a good one-electron reducing agent. It is soluble inmany polar

and non-polar media, and it generally forms diamagnetic cation [Cp2Co]+.
Cobalticinium salts are very stable to further oxidation; with strong oxidising
agents, the dimethylcobalticinium ion gives carboxylic acid without cleavage of
Cp-Co bonds:

Cobaltocene acts as a reducing agent towards alkyl halides:

Organic radicals add to cobaltocene. The η5-cyclopentadienyl ligand is thereby

converted into an η4-cyclopentadienyl ligand with attendant charge from an 19
VE to an 18 VE configuration:

Ferrocene and its derivatives:

Ferrocene undergoes many electrophilic reactions, more rapidly than benzene,

although they are limited by oxidation reactions with electrophiles that are
strong oxidants (H2SO4 or HNO3). Formylation and carboxylation gives only
monofunctionlization, because the functional group strongly deactivates the
ferrocenyl group. On the other hand, metallation and acylation reactions can be
followed by an identical reaction on the other ring leading to 1, 1’-disubstituted
17
derivatives, because the deactivation of the second Cp ring by substituent is
only modest.

Metalation of ferrocene:

The metalation of ferrocene with organolithium reagents is hampered by

problems with mono-, and multiple lithiation. The preparation of monolithium
ferrocene is done using SnBu3 and further forming organostannylferrocene.

1,1’-dilithioferrocene is obtained by reaction in presence of TMEDA.

The dilithio product precipitates as adduct of TMEDA having a complicated

structure and is used as such in further reactions.

18
19
20
APPLICATIONS OF FERROCENE:

Ferrocene has got many application in various fields of chemistry such as

catalysts, material science, drugs, polymers. It is used in materil science for
assembling charge transfer complexes(decamethylferrocene) and thermotropic
liquid crystals (example given below).

Ferrocenyl phosphines are used as ligand for catalysis. 1-1’-bis(diphenyl-

psosphino)ferrocene (dppf) is the best known ferrocenyl-based ligand in the
catalysis of many classic reactions and its chemistry and uses are numerous.

21
The redox property of ferrocene has been used to attech it to macrocycles
(example given below), cryptands, calixarenes and other endo receptors for
sensing, a area of chemistry developed by Paul Beer at oxford.

Ferrocenes are key components of polymers. Ferrocene containing polymers

have also been synthesized using cationic, radical or romp polymerization. They
are used to derivatize interalia electrodes, which can provide excellent redox
sensors. E.g. ring-opening polymerization of ferrocenophenes:-

Ferrocenes as many other cyclopentadienyl-metal complexes have been studied

as antitumor drugs or therapeutic agents. The redox activity of ferrocenyl group
may also add synergistic effects on cytotoxicity.

“Hydroxyferrocifen” related to anticancer drug tamoxifen in which a

ferrocenyl group has replaced a phenyl substituent with benefit on the
cytotoxicity.
22
 18 ELECTRON RULE

The 18-electron rule is a way to predict comparative stabilities of mainly

transition metal complexes. Not all the formulas we write down are stable in
nature and also their relative stabilities vary depending upon many factors. Like
in the case of simple compounds filled octet (noble gas structure) is a important
notion, for example CH5 doesn’t exist in nature as it requires a pentavalent
carbon atom. Stable compounds such as CH4, NH3, and H2O etc have noble gas
octet. So in this case we may call carbon to be following an 8e rule. This is due
to carbon using one s-orbital, and three p-orbital for its bonding. For filling
these 4 orbitals 8 electrons are required and we may consider 4-electrons comes
from four H-atom and rest 4-electrons comes from carbon atom. And here H
can be considered as 1e donating ligand to carbon.

The transition metals now have 1 ns, 3 np and 5 (n-1) d orbitals, we need
18-electron to fill these 9 molecular orbitals; some electrons to fill these orbitals
come from metal itself and rest comes from ligands attached to the metal. Some
of these 9 molecular orbitals are bonding, and some are non-bonding or
antibonding. Only limited number of combinations of metal and ligands fulfil
18-electron criteria. 18-electron rule is followed by a majority of complexes
(many exceptions also). The 18-electron electron structure brings a good
stability for complexes.

ELCTRON COUNTS FOR COMMON LIGANDS:

There are two models for counting the electrons in a complex: ionic model and
covalent model, both of which lead to exactly same results. They differ in the
way that electrons are considered to be coming from ligand or from the metal.
For example consider ferrocene:

Ionic model Covalent model

Fe 8e
Fe2 6e
2C5H5 6*2= 12e 2C5H5 2*5= 10e
18e 18e

23
The ways of assigning electrons are just models and moreover each bond
between two dissimilar atoms have some ionic and some covalent
characteristics. The covalent model is more appropriate for the majority of low-

valent transition metal complexes especially with unsaturated ligands. In the

same manner ionic model is more suitable for high-valent complexes with N, O,
or Cl ligands.
Some common ligands with electron donor power:
-
LIGANDS Formal charge No. Of e
donated
CO (bridging or terminal) 0 2
NO 0 3
PPh3 0 2
µ-CH2 0 2
µ-CR2 0 2
H (terminal or bridging hydride) -1 2
X (terminal) -1 2
µ-X -1 4
OR, SR (terminal) -1 2
(bridging) -1 4
NR2, PR2 (terminal) -1 2
(bridging) -1 4
Me or other alkyl -1 2
Cp -1 6

HAPTICITY:

The term hapticity is used to describe how a group of contiguous atoms of a

ligand are coordinated to a central atom. In most of the cases it is number of
ligand atoms bound to central metal atom. The Greek letter η (eta) is used to
show hapticity of a ligand in formula.
For example:

Ferrocene - bis(η5-cyclopentadienyl)iron

Uranocene - bis(η8-1,3,5,7-cyclooctatetraene)uranium

Zeise's salt - K[PtCl3(η2-C2H4)].H2O

24
SOME EXAMPLES OF 18-ELECTRON RULE:

Ionic model Covalent model

Ni2+ 8e Ni 10e

2*C3H5- 8e Ni 2*C3H5 6e
16e 16e

Mo 6e Mo 6e
Mo(C6H6)2
2*C6H6 12e 2*C6H6 12e
18e 18e

Fe 6e Fe 8e

2C5H5 12e Fe 2C5H5 10e

18e 18e

Mo4+ 2e Mo 6e

4*H 8e 4*H 4e
MoH4(PR3)4
4*PR3 8e 4*PR3 8e
18e 18e

Co3+ 6e Co 9e

2*C5H5 12e Co 2*C5H5 10e

18e
positive charge -1e
18e

4
CN Fe 8e
Fe2+ 6e
NC CN
6*CN 6e
6*CN 12e Fe
NC CN 4 negative charge 4E
18e
18e
CN

25
To predict total no. Of M-M bond in a polynuclear molecule:

This can be done in schematically as mentioned –

1. Determine total no. of electrons in the entire complex i.e. the no. of valence
electrons of metal plus total no. of electrons from ligand, say it A.
2. Subtract this no. From n*18 where n is no. Of metals in the complex, say it B.
3. a) B divided by 2 will give the total no. Of M-M bonds in complex

b) B divided by n will give number of electrons per metal.18e means no M-M

bond, 17e means 1 M-M bond, 16e means 2 M-M bond and so on.

Examples:

Fe3(CO)12 total electrons= 48 total M-M bonds: 54-48=6/2=3

bonds per metal=48/3=16; 2 bonds

similarly for Co4(CO)12 total e =60; M-M bonds=12/2=6 bonds per metal=3

[Cp(CO)2Mo]2 total e =30; M-M bonds= 6/2=3; bonds per metal = 3;

(µ-Br)2[Mn(CO)4]2 total e =34; M-M bonds= 2/2=1; bonds per metal = 1;

THE ISOLOBAL PRINCIPLE

The isolobal analogy was first proposed by Ronald Hoffman in order to

understand chemical bonds in more better way. Let us take an example of an
and , these two radical are very much similar in reactions and overall
chemistry. Both of these radicals have a single electron in a σ orbital pointing
in the direction opposite to that of substituents. Both dimerize rapidly and have
same radical-type chemistry.

H H
H

CH3 Mn(CO)5

Hoffman called these two fragments isolobal. Two fragments are isolobal if
they have same number of frontier orbitals, the same total number of electrons

26
in these orbitals and if the symmetry, energy and shape properties of these
orbitals are close. The way to indicate isolobality of two fragments is the
following:

H H
H

CH3 Mn(CO)5

Some important points about isolobality:

 If a fragment is isolobal with one of two isolobal fragments, it is also

isolobal with the other one. For example Cr(CO)5-, and Fe(CO)5+ are
isoelectronic with ; thus they are isolobal with .
 Since the main quantum number has only little influence on the shape of
the frontier orbital and also are isolobal with .
 Any 17-electron ML5 fragments such as Mn(PR3)5 is considered to be
isolobal with .

 The divalent fragments Fe(CO)4 and CH2 (carbene) are isolobal.

-
The CH3+, CH , SiR2, and SnR2, fragments are thus isolobal with
+ -
Fe(CO)4, as well as Ru(CO)4, Co(CO)4 and Mn(CO)4 .

The interest in isolobal analogy mainly concerns its structural implications.

The term isolobal is not only applied to fragments, but it is used also for
compounds made of isolobal fragments.

27