Assignment – 01

Organometallic chemistry

Name – Satyam Kumar

Entry no – 2022CYS7051

Introduction

Organometallic chemistry is the study of compounds containing metal-carbon bond or they form
metal-carbon bond during course of reaction , like Wilkinson catalyst it doesn’t contains metal-
carbon bond but form during course of reaction however all the compound which contains metal
carbon bond is not organometallic compound such as NaCN contains metal-carbon bond but it is
not organometallic compound . Organometallic chemistry has many practical application in
various fields such as pharmaceuticals , organic synthesis , petrochemical , material science . It
also plays a major role in catalysis chemistry it is used in many catalysis process such as
hydrogenation , hydroformylation , hydrocarboxylation , alkene polymerization. The discovery of
new organometallic compound provides a wide field fir research. Here we are going to focus on
some of the main group organometallic compounds like organomagnesium , oragnozinc and
organolithium.

Organolithium compound

Organolithium compound are less reactive than their analogous sodium and potassium this
behaviour is observed due to the small size of Li+ compared to those of other alkali- metal
cation result in much greater polarizing power for lithium ion i.e. , greater ionic potential ,
which is equal to Z/r , where Z is the ionic charge ( +1 in case of alkali metals ) and r is the
ionic radius in A° units the ionic potential for the following metal are as following Li+ , 1.66 ;
Na+ , 1.04 ; k+ , 0.76 ; thus organolithium compound to be more covalent than those of sodium
and potassium and much more soluble in organic solvent . Due to their solubility in organic
solvent, they are less prone to attack diethyl ether as a result organolithium has become a choice
for use in organic and organometallic synthesis when organometallic nucleophile is needed.
 Organolithium chemistry is developed by three giants of 20th century: Karl Ziegler, Georg
Wittig and Henry Gilman.

A . Synthesis of organolithium compounds by the reaction of metallic lithium with

organic halides: Karl Ziegler

Spencer and Price in 1910 firstly reported the reaction between metallic lithium and organic
halides. This reaction was carried out by taking equimolar quantity of organic halide and
lithium (in small pieces) were heated at refluxing quartz flask for 3 to 20 hrs, for these reaction
no solvent was used. Methyl iodide and bromobenzene which do not react with lithium under
this condition were heated with lithium in sealed tube at 250°C fir 6 hrs the white crystalline,
deliquescent solid was produced that reacted exothermically with water. They were considered
that the product was the mixture of respective organolithium and lithium halide.

Ziegler and Colonius repeated the experiment of Spencer and Price and found that under their
condition not even trace amount of organolithium compound found . Schlenk and Holtz in 1917
give the process for preparation and separation of alkyl and aryllithium compounds by metal
displacement reaction. This route however did not used for general application , sine it requires
prior preparation of diorganomercurials many of which are toxic. The discovery by Ziegler and
Colonius that organolithium compounds could be prepared by reaction of metallic lithium with
organic halides , bromides and specially chlorides in benzene was the needed breakthrough . With
n-butyl bromide in ether n-C4H9 Li was formed in 15% yield . Where as n-butyl chloride react with
lithium in ether to give n-C4H9Li in 55% yield after 20 hrs . If reaction carried out in benzene, 45
% yield of n-C4H9Li was obtained when n- butyl bromide was used , with n- butyl chloride in
benzene it will give 67% yield for n-C4H9Li . phenyl lithium is is weaker base than the alkyllithium
thus diethyl ether used for solvent for the C6H5Br(I)/Li reaction , which start vigorously and
required external cooling and give yield of 75% for phenyllithium . Lithium metal containing a
small concentration of sodium was found than sodium free lithium in in preparation of
organolithium reagent . When lithium containing 2% sodium was used in pentane will give 80%
yield for t-BuLi .Freeman and Hatchinson found that reaction of alkyl halides with excess of
lithium p,p-di-tert-butylbiphenyl radical anion salt in THF at – 78°C gave RLi reagents in 93 to 95
% yield. Reduction to RH was major competing reaction when Li+[di-tert-butylanthracene]- was
used .
 CH3CH2OCH2CH3 + RLi → CH3CH-(Li)+OCH2CH3 + RH

CH2=CH2 + CH3CH2OLi

The temperature at which selected organolithium reagent could be used in THF were found to be
as follows : CH3Li,0°C ; n-C4H9Li , below – 35°C ; C6H5Li, 0 to -10°C .

B. Synthesis of organolithium reagent by the lithium-halogen exchange reaction.

Lithium halogen exchange reaction is very useful and widely utilized procedure for the preparation
of organolithium reagent , in Gilman’s paper it is called lithium -halogen interconversion reaction.

RLi + R’X ⇌ R’Li +RX

When R is alkyl and R’ is aryl the equilibrium shift towards right and thus useful for preparation
of aryl lithium reagent . The lithium -halogen exchange reaction doesn’t takes place with the less
reactive alkyl chloride, instead dehydrochlorination via alpha metalation takes place, in case of
aryl halide, bromide and iodide Lithium – halogen exchange reaction work best.

Lithium -halogen exchange reaction was reported by Wittig in 1938 he found that when
phenyllithium metalated react p-bromoanisole give lithium -hydrogen exchange and in same
way it react with 1,4 and 1,3-dimethoxy benzene but when phenyllithium react with1,3-
dinethoxy-4,6-dibromobenzene in diethyl etherate room temperature react differently and
give lithium-bromine exchange.
During the study of the reaction of phenyllithium with halogenated benzene In case of
fluorobenzene the first example of reaction that proceeded through benzyne mechanism was
discovered the ortho lithiation of fluororbenzene followed by LiF elimination and addition of
phenyllithium to benzene. Three months after Wittig paper had been published, Gilman reported
their independent discovery of the reaction of o-bromoanisole with n-butyllithium which give o-
anisyllithium .
Aryl iodide were more reactive than aryl bromide and aryl chloride , fluoride in most cases didn’t
undergo Lithium -halogen exchange reaction with n-butyllithium.

Organolithium compound used as initiators for polymerization of 1,3-diene polymerization

and styrene. Ziegler in his investigation using alkyllithium compounds to activate c=c
bonds, alkyllithium compounds initiated the polymerization of isoprene to give cis
polymers with properties resemblance with natural rubber . n-sec and n-tert-butyllithium
are used as catalyst

Organomagnesium (Grignard reagant)

Grignard reagent is the most widely used organometallic reagent during the past 100 years. It is
discovered by victor Grignard at University of Lyon in France in 1900 .their ease in preparation
and their broad application in organic and organometallic synthesis made it an instant success .
Victor Grignard awarded a Nobel prize in chemistry in 1912., it is prepared by reacting organic
halide with metallic Magnesium in ethereal solution or THF, excluding any moisture or oxygen
because Grignard reagent is highly reactive .

RX + Mg → RMgX

In Grignard reagent (X= Cl ,Br ,I) reaction between magnesium and fluorinated compound is
difficult because of following reason strong bond between carbon – fluorine , due to short bond it
is difficult for magnesium to approach and attack the carbon atom ,fluorine is highly reactive
compound it will react vigorously with many organic compound and that is why fluorinated
Grignard reagent does not form ed easily. Wilhelm Schlenk and hi son discovered that more than
one magnesium-containing species exist in the diethyl ether solution of a Grignard reagent due to
redistribution of substituents on magnesium it ends up in equilibrium with two symmetrical species
magnesium dihalide and diorganomagnesium and this equilibrium named as Schlenk equilibrium.

2RMgX ⇌ R2Mg + MgX2

The species that contains Mg – halogen bonds can be precipitated by addition of 1,4-dioxane from
Grignard reagent solution in diethyl ether. Eugene Ashby and Frank Walker at georgia Institute
of technology found that monomeric , dimeric and higher oligomeric species were present
depending on the halogen and the solvent and substituents on the magnesium atom and this is
observed due to the tendency of halide to form bridges between magnesium atom . Toney and
Stucky isolated crystals of dimeric species from the solution of C2H5MgBr in di-n-butyl ether by
addition of this solution to triethylamine.

Complicated structure of RMgX is determined by X-ray crystallography of crystalline compound.

There are so many factors that arises question of the constituent of Grignard reagent in ethereal
solution such as the Lewis basicity and steric property of ether solvent, electronegativity and size
of halogen atom, the nature and steric properties of organic substituents on magnesium atom .
These will affect the magnitude of equilibrium constant of the Schlenk equilibrium and the extent
of Mg – X – Mg bridging.

Grignard reagent are extensively used in small to moderate level of industrial process it is highly
reactive to air and moisture that is why they are prepared and consumed in situ. Mostly they react
as nucleophilic reagent due to the partial negative charge developed on carbon.

Two special topics of current interest are

• The preparation of highly functionalized organomagnesium reagent by Paul knochel and

his co- workers at the University of Munich by halogen – magnesium exchange this new
reagents headed a new spectacular dimension of Grignard reagent chemistry.
• The use of cross coupling of Grignard reagent with organic halides to synthesis olefins,
styrene’s , 1,3- dienes and binary derivatives , the cross coupling of Grignard reagent with
 vinylic halides was discovered by Morris Kharasch and Charles Funchs at the University
of Chicago.
Organozinc compounds

Edward Frankland while trying to prepare and isolate ethyl radical by taking finely granulated
zinc and ethyl iodide in a sealed glass tube accidentally formed the first ever main group
organometallic compound diethylzinc , His goal was to prepare and isolate ethyl radical. Organic
chemistry in the first half of the 19th century is disorganised state chemist of that time proposed
many theory to rationalize and systematize the known types of organic compound one such theory
is alcohol radical that is proposed by Liebig and Kane . Berzelius was an enthusiastic supporter of
radical theory. For instance he has considered acetic acid to be a conjugated compound composed
of methyl radical and CO2H (on the basis of his atomic weight scale C=6 and O=8) . Cacodyl
radical of Bunsen (CH3)4As2 (later (CH3)2As) was regarded by the chemist of that day as the first
radical that actually has been isolated. Hermann Kolbe and Frankland while working together they
carried out the action of potassium on C2H5CN, a rather violent reaction which proceeded with
flashes of light and rapid gas evolution they thought the gas is methyl but on analysis actually it
was actually ethane. After that Frankland moved to England and took a position as science master
at newly founded Queen-wood college, he carried out his first experiment aimed to isolate ethyl
radical. for this the reaction is carried out in sealed tube by reacting ethyl iodide and potassium
this reaction also was rather violent and the gaseous product were not expected ethyl but rather
methyl. Stimulated by the reaction That Bunsen bad applied successfully to isolate what
considered to be the cacodyl radical at that time.

2(CH3)2AsCl + Zn → (CH3)4As2 + ZnCl2

Frankland Set up the reaction between C2H5I + Zn in a sealed tube, no reaction occurs Until 150°C
but at 200°C the reaction proceeded with tolerable rapidity giving white crystal and leaving a
colourless mobile liquid. the tube containing reaction mixture remained sealed for some month
due to lack of eudiometer required to analyse the reaction mixture, Frankland return to Marburg
to obtain his Ph.D. Under Bunsen guidance. The study of C2H5I / Zn reaction result published
both in German and in English, and this work served as his Ph.D. dissertation at University of
Marburg. Bunsen great expertise in gas analysis which Frankland has mastered while at Marburg
help him to study reaction mixture of sealed tube on opening the sealed tube large volume of gas
was evolved and the mobile liquid phase disappeared. On collection and analysis of these gases
the result is as following ethylene (21.70%), ethyl (50.03%), methyl (25.79%) , nitrogen (2.48%)
all by volume .Frankland firmly believed that he has produced the ethyl radical , later it is observed
that these gases are not the ethyl and methyl radicals at all but rather their dimers the saturated
hydrocarbons ethane and n-butane . Frankland concluded that iodine of zinc combines with small
portion of methyl forming a white crystalline compound probably of definite composition but he
doesn’t make the connection that this crystalline solid contains an Organozinc compound. Thus
ethylzinc iodine and diethylzinc were the first alkyl zinc compound that Frankland had prepared
probably in sealed tube when reaction mixture heated to 200°C giving real ethyl radical through
homolytic Zn-C scission the ethyl radical dimerized giving n- butane and on disproportionate
giving ethane and ethylene. On seein g the green – blue flame several feet long shoot out of tube
on pouring few drop of water professor Bunsen ,who had suffered from arsenic poisoning during
his research on cacodyl the shoot is observed due to the impurities by arsenic in zinc .Frankland
now has explanation for the observation made in his previous study of reaction between zinc and
ethyliodide, by similar method he also had prepared zinc ethyl which is somewhat less reactive
towards water. it’s reaction by Frankland written as

C4H5Zn + HO → ZnO + 2(C2H3)

By seeing this result Frankland suggested that the reaction of ethyl iodide with arsenic and tin also
give radical. Frankland wrote his full papers on dimethyl and diethylzinc Thus merit closer
examination because they illustrate Frankland experimental ingenuity, he is an accomplished
designer and maker of special laboratory glassware, but his other metal apparatus type such as
autoclaves are noteworthy. The isolation of the volatile, pyrophoric, extremely moisture sensitive,
and I’ll smelling dimethylzinc in high purity was no trivial task to achieve this he has designed the
apparatus. The sealed tube synthesis of the dialkylzincs were limited to the preparation of small
quantities in low yield. For the preparation of large quantities, he with help of an engineer named
Nasmyth constructed more sturdy metal equipment. Frankland started making official monthly
analysis of London water supply from 1868 to 1874, he served on the royal commission on river
pollution . He become very interested in the analysis of water, developing new methods for
detection of carbon and nitrogen in water . Fir his important work as a member of the royal
commission on water analysis and purification, Frankland was knighted in 1897.

Reactions of Organozinc compounds

Many reaction are carried out with help of Organozinc compound in many of the reaction it acts
as intermediate such as Simon- smith reaction , reformatsky reaction , Frankland – Duppa reaction
Barbier reaction , fukuyama coupling , Negishi coupling etc here we are going to discus few of
them

• Simmons – smith reaction

Gladstone and tribe in 1873 discovered that zinc metal could be activated by adding copper . This
result in higher rates and in high yields. Zn/Cu couple is more important in the case of CH3I/Zn
reaction this point was addressed by Renshaw and Greenlaw, whose Zn/ Cu couple was very
effective in the preparation of (CH3)2Zn. Further using this concept H.E. Simmons and R.D. smith
generated ICH2ZnI in situ which react with unsaturated carbohydrate to give cyclopropane.

• Reformatsky reaction

Thus reaction named after Russian chemist Sergey nikolaevich Reformatsky . This reaction
occurs between alpha- halo ester and ketone and aldehyde is converted into beta- hydroxy –
ester.
 REFERENCES

1. Wittig, G.; Pockels, U.; Dro¨ge, H. Ber. Dtsch. Chem. Ges. 1938, 71, 1903.
2. Gilman, H.; Langham, W.; Jacoby, A. L. J. Am. Chem. Soc. 1939, 61, 106.
3. Ziegler, K.; Gellert, H. G. Liebigs Ann. Chem. 1950, 567, 179.
4. Schlenk, W.; Schlenk, W., Jr. Ber. Dtsch. Chem. Ges. 1929.
5. Kharasch, M. S.; Reinmuth, O. Grignard Reactions of Nonmetallic Substances;
PrenticeHall: New York, 1954.

6. Frankland, E. J. Chem. Soc. 1850, 2, 263.

7. Frankland, E.; Duppa, B. F. J. Chem. Soc. 1864, 17, 29.