Syllabus

✓ Introduction, general formula and examples of organolithium, organocopper

and organocadmium compounds
✓ Nature of Metal-Carbon bond
✓ Grignard reagent
✓ Preparation (using haloalkane and haloarene)
✓ Reaction of Grignard reagent with water, aldehydes and ketones( preparation
of primary, secondary and tertiary alcohols), carbon dioxide, HCN, RCN, ester
and acid chloride

❖ Organometallic compounds are those compounds in which the carbon

atoms of organic groups are bonded to metal atoms. The linkage (M – C)
may be either 𝝈-type or π-type.
❖ The metal is less electronegative than the carbon, so the carbon metal bond
is highly polar, with carbon pulling electron from metals (R𝛿- – M𝛿+).
❖ The organometallic compounds are also known as non-stabilized
carbanions.
❖ (C3H7O)4Ti [Titanium(IV) isopropoxide], RCOONa etc. are not considered as
organometallic compound due to lack of metal to carbon bond.
❖ C6H5Ti(OC3H7)3 [Phenyl titanium triisopropoxide) is considered as
organometallic compound because a metal to carbon bond is present.
❖ This class of compound is named by prefixing the name of the metal with the
organic radical and the name is written as one word.
Classification of organometallic compounds on the basis of nature of
the metal to carbon bond:
1. Sigma (σ) bonded organometallic compounds:
Organometallic compounds having metal-carbon σ –bond are called sigma
bonded organometallic compounds.
Examples: Ethylmagnesium bromide (C2H5MgBr), Ethyl lithium (C2H5Li), etc.

2. Pi (π) bonded organometallic compounds:

Organometallic compounds having metal-carbon π –bond are called pi-
bonded organometallic compounds.
Examples: Zeise’s salt i.e; K[PtCl3(C2H4)], Ferrocene i.e; Fe(C5H5)2, etc.

❖ The first synthetic organometallic compound is Zeise’s salt , i.e; K[PtCl3(C2H4)].

Organometallic compounds are divided into;

i) Symmetrical:
Example: CH3-Hg-CH3 (Dimethyl mercury)

ii) Unsymmetrical:
Example: CH3-Hg-CH2CH3 (Ethyl methyl mercury)

iii) Mixed:
Mixed organometallic compounds are those compounds in which a metal is
bonded with more than one identity of organic or inorganic constituents.
Example: C2H5-MgBr (Ethyl magnesium bromide)
Organolithium compounds
▪ Organolithium reagents are the organometallic compounds having general
formula R-Li (R is an alkyl group) or Ar-Li (Ar is an aryl group).
▪ They contain C-Li bond.
▪ The bond is covalent but strongly polar in nature.
Examples:
CH3-Li (Methyl lithium), C2H5-Li (Ethyl lithium), C6H5-Li (Phenyl lithium) etc.
▪ They are used to transfer the organic group in synthetic steps (organic
synthesis).
▪ They are used as an initiator for anionic polymerization and applied in
asymmetric synthesis in the pharmaceutical industry.

Preparation of organolithium reagent

• Organolithium compounds possess more ionic character than the Grignard
reagents because of the smaller size and high polarizing power.
• Organolithium compounds can be prepared in a manner similar to that of
Grignard reagents.
General reaction: RX + 2Li → RLi + LiX

Examples:

▪ Pentane or hexane is used as solvent for this reaction.

▪ One of the most valuable reactions of alkyl lithium is its use in making lithium
diorganocopper compound, R2CuLi, called Gilman’s reagent. The name is
given after its discoverer Henry Gilman.
▪ Henry Gilman is an American organic chemist known as the father of
organometallic chemistry.
Organocopper compounds
Organocopper compounds are the compounds that contain carbon- copper
bonds. There are of two types:

i) Organocopper compounds /alkyl or aryl copper (R-Cu)

Examples:
CH3-Cu (Methyl copper), C2H5-Cu (Ethyl copper) etc.

ii) Lithium organocuprate (R2CuLi): Gilman’s reagent

Example:
(CH3)2CuLi (Lithium dimethyl cuprate)

Preparation of Organo copper compounds and Corey-House Synthesis

Alkyl halides react with lithium in dry ether to form alkyl lithium.
R-X + 2Li ⇾ R-Li + LiX

This alkyllithium reacts with CuI to give Dialkyl Lithium Cuprate or Lithium Dialkyl
Cuprate known as Gilman reagent.

2R-Li + CuI ⇾ R2CuLi + LiI

This dialkyl lithium cuprate reacts with alkyl halide to give alkane and the
reaction is known as Corey-House synthesis.

R2CuLi + R’-X ⇾ R-R’ + R-Cu + LiX

Organocadmium compounds
They are the compounds having carbon-cadmium bonds. Their general formula
is R2Cd.
Examples:
(CH3)2Cd (Dimethyl cadmium), (C2H5)2Cd (Diethyl cadmium) etc.
 Nature of Metal carbon Bond
➢ In organometallic compounds, carbon is bonded with metals like lithium,
copper, magnesium, cadmium, zinc etc.
➢ The metal carbon bond in organometallic compound is generally covalent.
➢ Carbon is more electronegative than most of the metal atom. Therefore
bond between carbon and metal is polar where metal atom carries partial
positive charge (𝛿+) and carbon carry partial negative charge (𝛿 -).
Electronegativity values of different elements

Li- 1.0 C-2.5

Na-0.9 Mg-1.2 Al-1.6

K-0.8

➢ Magnesium has an electronegativity of 1.2 compared with 2.5 for carbon.

This large difference in electonegativity makes the carbon-magnesium bond
very polar. (The C-Mg bond is about 52% ionic).
➢ The following sequence indicates the variation in ionic character in carbon-
metal bond.

C-K > C-Na > C-Li > C-Mg > C-Zn > C-Cd

Grignard Reagent
• Organonmagnesium halides are called Grignard Reagents in honor of
Francois Auguste Vitor Grignard for the discovery of this versatile organic
compound.
• Alkyl or Aryl magnesium halides are commonly known as Grignard Reagent.
• Grignard Reagents were discovered in 1900.
 Victor Grignard, in full François-Auguste-Victor
Grignard, (born May 6, 1871, Cherbourg,
France—died Dec. 13, 1935, Lyon), French
chemist and co recipient, with Paul Sabatier, of
the 1912 Nobel Prize for Chemistry for his
development of the Grignard reaction. This
work in
organomagnesium compounds opened a
broad area of organic synthesis.

Preparation (from Haloalkane and Haloarene)

Grignard found that when magnesium turnings are stirred with an ether or
tetrahydrofuran (THF) solution of an alkyl or arylhalide, an exothermic reaction
occurs. Magnesium, which is insoluble in ether, disappears as it reacts with the
halide to give solutions of ether soluble Grignard reagents.
➢ The carbon-halogen bond is broken and both the alkyl or aryl group and
halogen become bonded to the magnesium.
➢ The order of reativity of alkyl halides with magnesium is

RI > RBr > RCl

➢ The two ethers most commonly used in Grignard preparation are diethyl
ether (Et2O) and cyclic ether tetrahydrofuran (THF- C4H8O).
➢ Grignard reagents are seldom isolated but are used for further reactions in
ether solution.
➢ A Grignard reagent forms a complex with its ether solvent.

Following precautions should be taken during its preparation.

• The reagents used should be pure and perfectly dry as moisture and air
rapidly destroy the reaction by protonolysis or oxidation.
• When Grignard reagent comes in contact with water, it converts to alkane.
R-MgX + H2O → R-H + Mg(OH)X
Grignard reagent Alkane Basic magnesium halide

• All the reagents should be anhydrous and apparatus must be oven dried.
• There should not be naked flames nearer.
• Ether should be used as the solvent because it has no acidic protons, so
Grignard reagent is stable in ether and ethers are great solvating agent.
Reactions of Grignard reagent
1) With water:
When Grignard reagent is hydrolysed with water, alkanes are obtained.

2) With alcohol:
Alcohols react with Grignard reagent to form alkane.

3) With aldehydes and ketones:

When aldehydes and ketones are reacted with Grignard reagent, addition
product is formed which upon acidic hydrolysis give alcohols.

i) Formaldehyde/Methanal yields primary alcohol:

ii) Aldehyde other than formaldehyde yields secondary alcohol.

iii) Ketone yields tertiary alcohol.

4) With carbon dioxide/carboxylation reaction:

Grignard reagent reacts with carbon dioxide in presence of dry ether to give
addition product which upon acidic hydrolysis gives carboxylic acid.
5) With acid chloride:
Acid chloride reacts with Grignard reagent and forms ketone which further
reacts with Grignard reagent and yields tertiary alcohol.

6) With esters:
Esters (except those of formic acid) react with Grignard reagent to give ketones,
which further react with Grignard reagent to give tertiary alcohols.
7) With hydrogen cyanide:
Reaction of Grignard reagent with HCN followed by acid hydrolysis gives
aldehyde.

8) With alkane nitrile/alkyl cyanide:

Reaction of Grignard reagent with alkyl cyanide followed by acid hydrolysis
gives ketone.