Chapter 5

Organometallic Compounds
An organometallic compound is defined as a compound which contains a direct
carbon-metal bond.
-Metal or C-M
(Carbon-Metal Bond)
where M-K, Na, Li, Ca, Mg, Al, Zn, C£, Sa, Pb, Hg etc.
Organometallic compounds are named by simply adding the name of the metal (M) to
that of the organic group which may be alkyl, alkenyl or aryl.
Examples :.
H
GH,
H-i Za<
GH,
methyllithium diethylinc triethyialuminium
GH
H CaC-K
potasstum acetylide
CH, pheayimagocsium chloride
tetraethyllead
It may be noted that the above definitjon of organometallic compounds excludes subs.
tances such as sodium methoxide and sodium, acetate in which the metal is not directly bonded to
carbon. 99142

HONa H,C 0Na

sodiutn acetate
H
sodium methoxide
Here the metal is linked to carbon through oxygen and these compounds are not organo
metallic compounds.
Ionie Character. Organometalic compounds could be represented as I or I.
--M

0% lonic 100% lonicpartial lonjc character

(covalent) (between 0% and 100%)
The structure I is covalent, while II is ionic. In other words, I is zero per cent ionic and
II is hundred per cent ionic. The true situation is somewhere in between which is represented by
336
 337
Orgenometalle Compounds
IL. The extent of the ionic character of C-M bond depends on the clectropositive natureof the
more ionic tne carbon-metal bond.
metal. In general, more electropositive the metal the
Table. Per cent lonic character of some Carbon-Metal bonds

C-M % lonic C-M % lonic C-M % lonic

C-K 51 C-Mg 35 CSn 12

C-Na 47 C-AI 22 CPb 12

C-Li 43 C-Zn 18 C-Hg

C-Ca 43 CCd 15

The reactivity of organometallic compounds increases with the ionic character of the
cM bond. Thus highily ionic compounds such as organosodium (RNa) and organopotassium
(RK) cOmpounds react
are amongwith
violently
the most reactive
water, are
organometallics.
nonvolatile and do
Theydissolve
not
are spontaneously
readily in infam
nonpolar
mable in air,
solvents. On the other hand morerelatively
covalent stable
compounds like tetracthyllead and dimethyImercury.
in air, volatile and soluble in nonpolar solvents
(CH),Hg, are far less reactive,
like hydrocarbons and ether. The organometallic compounds of intermediate ionic character such
as thoseof lithium and magnesium are of greater interest to the Organic Chemist. These are
relatively easy to prepare and handle, and are useful synthetic reagents.
GRIGNARD REAGENTS
Of all the organometallic compounds known, organomagnesium halides (RMgX) or Grig
nard Reagents are the most important. They are s0 named after Victor Grignard who dis.
covered them and developed their use as synthetic reagents. They occupy pride of place in
organic synthesis by virtue of their versatility and wide application. Almost all classes of organic
compounds can beprepared from them. Grignard carned one-half ofaNobel Prizein 1912for
his remarkable contribution to synthetic organic chemistry.
The general formula for Grignard reagents can be writen as
R-Mg X or R-MgX or RMgX
where R = alkyl, alkenyl, alkynyl or aryl group.
X= Cl, Br or I
Organomagnesium fluorides are 'nöt kHöwn.
Examples :
MgBr
CGH,-Mg-Br
ethylmagnesi um
CH,-CH-CH CH,
2-butyimagneaium bromide
CH,-CH-Mg Ci
bromide vinyimagneium chloride
-Mg-Br
CH,=CHCH, -Mg-1
allylmagnesium iodide
CH, CaC-Mg-Br
propynylmagnesium
bromide phenyimagnesium bromide
Preparation. Grignard reagenis'are prepared in the laboratory by the action of alkyl
halides on magnesium metal in the presence of dry ether.
dry ether
R-X + Mg R-Mg-X
alkyl halide Grignard reagent
(alkylmagnesium halide)
dry ether
e.g., CHI + Mg CH Mg-I
methyl iodide methylmagnesium iodide
For a given alkyl group (say R), the ease offormation of the Grignard reagent is in the
ordar DT RRr RC
 339
Orgonometallk Compounds
In actual practice a Grignard reagent is produced by dropping a solution of the alkyl
halide in dry ether into the reaction flask containing magnesium ribbon suspended in dry ether.
The ether solution of the Grignard reagent thus obtained is used immediately in the flask in which
it is prepare.
In the preparation of Grignard reagents care must be taken that all the apparatus and
reactants are absolutely dry. The moisture or any other impurities present will react with the
Grignard reagent produced. Thus even traces of moisture or impurities prevent the formation of
Grignard reagent.
The magnesium needed for the Grignard reaction is in the form of short lengths (5mm)
of ribbon which is dried by placing in a desiccator for a long time. Ether is washed with water
to remove any ethanol and then allowed to stand over fused CaCl, overnight. It is then distilled
to get absolutely anhydrous ether free from ethanol.
over sodiumfollowed Alkyl halide is purified by
distillation by allowing it to stand over anhydrous CaCl, or MgSO0, for a few hours.
Procedure. The apparatus used for the preparation of Grignand reagent is assembled
as shown in Fig. 15-3.
jELECIRJC
MOrOR

STIRRER

CaCl1 AIR TIGHT Caclz

3EAL

CHyI +DRY
ETHER
TO SINK

-ETHER

Fig 153. Preparation of Methylmagpesium iodide.

Magnesium ribbon cut into small pieces is suspended in dry ether placed in the three
necked round-bottom fask. In the dropping ml funnel is placed approximately 1:1 mixtureintoof
methyl iodide and anhydrous ether. Add 2-3 of the solution from the dropping funnel
the reaction flask and wait till the reaction commençes. When the reaction starts, the ether
becomes cloudy and also begins to boil gently. 'Further, there are visible signs of attack on
magnesium. If the reaction does not start, drop one or two crystals of iodine into the flask. Then
the reaction would start. Once the reaction has commenced, the addition of solution (CH,I in
ether) from the dropping funnel is maintained at such a rate that the ether in the flask refluxes
gently. When the reaction is complete, a clear sloution of to get thereagent
the Grignard in ether is
obtained. This is then treated in situ with various substances desired synthetic
products.
MECHANISM OF FORMATION. The formation of Grignard reagents by the above
procedure probably occurs via free radical mechanisn as given bellow.
2R-X + Mg’ R-R + MgX
Mg + MgX, 2MgX
R-X + MgX ’ R+ MgX,
R + MgX’ R-Mg-X
ORGANOLITHIUM COMPOUNDS
In these compounds carbon atom of the hydrocarbon group is directly bonded to
lithium. For example,
H H
-Li
HCLi HC-C-i CH,CH,CH,--Li
H HH H
methyllithium ethyllithium n-butyllithium phenyllithium
Alkyllithiums behave much in the same way as Grignard reagents, but with enhanced
reactivity. Therefore, they are now being increasingly used in organic synthesis.
Preparation. Organolithium compounds are obtained by the reaction of alkyl halides
with metallic lithium in ether in an inert atmosphere of nitrogen or helium.
dry etber
CH,-Br + 2Li CH,-Li + LiBr
D-methyl -10, N, methyl
bromide lithium
dry etber
CH,CH,CH,CH,
n-butyl bromide
-Br + 2Li CH,CH,CH,CH, -Li + LiBr
-10, N, n-butyllithium
Phenyllithium can be prepared by the reaction of lithium on bromo- or iodobenzene in
ethereal solution.
-Br ether
+ 2 Li + LiBr
phenyi bromide, pbenylithium
bromobenzene
ORGANOZINC COMPOUNDS
Organozinc compounds are less reactive. than Grignard reagents and are sometimes used
in organic synthesis in preference to the former. The two derivatives of zinc discovered by
Frankland (1849) are :
CH,dimethylzinc
Zn CH, GH Za GH,
diethyizinc
Preparation. Dialkylzincs are prepared by heating alkyl iodides with zinc in an atmos
phere of CÔ,, and then distilling the product (alkylzinc iodide) in an inert atmosphere of Co,.
CO,
C,HI
etbyl iodide
Zo CGH,-Znl
ethylzinc iodide
CO
2C,H,-Zal GH,ZaCH, + Zal,
distil ietbylzioe
Dimethylzinc can also be prepared similarly
ess unnleas ioui
TETRAETHYLLEAD (TEL)
CH,CH,
CH,-CH,-Pb CH, CH, or (GH,-),Pb
CH, CH,
It is perbaps the most important organometallic compound which finds wide use in
commerce under the name TEL.
Preparation. (1) It is conveniently prepared by the action of ethylmagnesium iodide
with lead chloride.
14
2PbCI, + 4C,H-Mgl (GH,-)Pb + Pb + 4MglCI
tetraethyllead

349
Orgonomatellic Compounds
(2) On a commercial scale it is mostly made by the reaction of ethyl chloride with sodium
lead alloy (Na, Pb). (GH,-),Pb + 4NaCl
4C,H, CI+ Na,Pb tetraethyllead

Use as Antiknock. Tetraethyllead (1 to 3 ml per gallon) serves as an antiknock' for gaso

line (petrol) used in automobile engines. The rate of combustion reaction of gasoline hydro
carbons increases sharply under high compresion which causes knocking of the engine. Viewed
chemically, over-rapid combustion of motor fuel under high pressure produces free hydrocarbon
radicals and knocking is due to the chain reactions set up by these radicals. The antiknocking
it produces ethyl free radicals which act as
property of TEL is probably explained by the fact thatgasoline
'radical traps' for the radicals (R:)produced from and chain reactions are thus termi
nated.
(CGH,),Pb 4CH, + Pb
ethyl radical
R (from gasoline) + CH, R-CH,CH,
alkane

The combustion of leaded gasoline' produces lead oxide which deposits in the exhaust
bromide is also added
pipe of the engine. To avoid this, a small amount of ethylalongwith to gasoline to
convert lead oxide into volatile lead bromide and it escapes the exhaust gases. However,
lead compounds are toxic so that the automobile exhaust gases pose a big health hazard in large
cities.