Experiment No: 3

Synthesis of Schiff Base and Metal

Complexes: Structure Interpretation by IR
and 1H NMR

Scheme-1
First week we will synthesize Schiff base and second week we will use this ligand to make metal
complex (It is optional). Before going to put second step you should purify the previous
compound i.e Schiff Base.

Introduction:
Hugo Schiff described the synthesis of Schiff base using a condensation reaction between
an aldehyde and an amine in 1864.1 Schiff base ligands can coordinate with various metals
through imine nitrogen and another group, usually linked to the aldehyde. Schiff bases contain
azomethine nitrogen (C=N).
Synthesis of Schiff bases and metal complexes are always an interesting field in
chemistry. These complexes have been studied extensively in coordination chemistry,
polymerization chemistry, medicinal chemistry etc.
Schiff bases are able to stabilize many different metals in various oxidation states and
thus can control the performance of metals in large varieties catalytic transformations. Chiral
Schiff bases can be synthesized either by chiral aldehyde or chiral amine. Chiral Schiff base can
transfer the chiral information to produce a non-racemic product through catalytic process.

In medicinal chemistry or pharmacological research the design of metaldrug complexes

is a great interest. Metal complexes as pharmaceutical agents are known to improve the activity
of the drugs and decrease their toxicity during metabolism.2 C=N linkage is essential for
biological activities. Several azomethine have been reported to possess remarkable antibacterial,
antifungal, anticancer and antimalarial activities. Metal complexes with Schiff bases enhance the
anticancer activity in comparison to the free ligand.
Few examples of Schiff base metal complexes are listed in below.

Day-1 Experiment: Synthesis of Schiff base

You will be given two different carbonyl compounds namely salicaldehyde and 2hydroxyacetophenone. That means you will be synthesizing two different sets of ligands L1 and
L2 respectively.

Chemicals require:
Salicaldehyde (MW: 122.12; d:

Ethylenediamine (MW: 60.10; d:

1.146g/mL)

0.90 g/mL) (1 eqiv)

EtOH (Solvent)

/2-hydroxyacetophenone (MW:
136.15) (2 equiv)

Procedure:
Step-1: Take salicaldehyde/2-hydroxyacetophenone (0.05 mol) in 15 mL of EtOH in 100 mL rb
fitted with reflux condenser and guard tube.
Step-2: Add ethylenediamine (0.025 mol) in the reaction mixture.

Step-3: Immediately ppt will form. (Note down the colour).

Step-4: To ensure the completion of reaction, stir the reaction mixture at 40-50 C for 45 min to 1
h.
Step-5: Check TLC after 30 min. If it shows full consumption of starting material you can stop
the reaction.
Step-6: Filter the ppt using a Buchner funnel and wash with EtOH.
Step-7: Dry the compound in high vacuum. Calculate yield.
Step-8: Keep aside few crude compound to record IR spectrum to check C=N stretching
frequency. Latter you can check with crystallized product.
Step-9: Purify the remaining compound by recrystallizaton using hot EtOH. Pure compound will
be submitted for 1H NMR.

Product Analysis:
1

H NMR:

IR:

Discussion:
Draw a table mentioned in below.
Entry

Structure of Schiff Base

L1

L2

%Yield

IR

H NMR

Table-1

Day-2 Experiment: Synthesis of Ni (II), Cu (II) and Co (II) Complexes using

Schiff base (Optional)
1.

You have already synthesized two different sets of ligands L1 and L2. You will make Ni,
Co and Cu(II) complexes with ligand L1/L2 respectively.

2.

For todays experiment details procedure will not be provided. You have to follow the
below information and put reaction as your own way to isolate the product.

3.

Few papers regarding complextion with Schiff bases are mentioned in reference section.
Before coming to lab go through those papers to gather knowledge about the general
complextion procedure.

4.

Each group should collect data from others

5.

Metal: Ligand ratio should be 1:1. Calculate the amount (mention mmol also). Try to put
reaction in 1 g scale

6.

In reaction vessel take respective amount of Schiff base (1 equiv) and dissolve it with
MeOH. Note it down the amount of MeOH. If require you can heat it to dissolve the
compound.

7.

Now dissolve the respective metal salt using distilled water. Note it down how much
solvent require dissolving metal salt.

8.

Add metal solution into reaction vessel which contains ligand solution. Slow addition is
advisable. You can use a dropper/or dropping funnel. Note it down colour change during
addition.

9.

To ensure the completion of reaction reflux the reaction mixture for 1 h.

10.

After one hour filter the product. Dry in high vacuum. Calculate the amount of crude
product.

11.

Find out an appropriate solvent to recrystallize the product. Pure product will be submitted
for 1H NMR. You have to compare the 1H NMR spectrum of complex with 1H NMR
spectrum of pure ligand. Indicate the difference with explanation.

12.

You have to record IR spectrum for pure compound too with proper explanation and
comparison with free ligand.

Discussion:
Tabulate the synthesis of metal complexes using two different ligands mentioning their colour
and yield.
Entry

Ligand

Metal

Complex
(Colour)

Table-2
Compare the spectral data of free ligand with metal complex as mentioned in Table-3

Yield

Structure of

Stretching frequency of

Structure of metal

Stretching frequency

Ligand

C=N for free ligand

complex

of C=N for metal

complex

Table-3
Write down the conclusion.

Reference:
1.

(a) T. P. Yoon and E. N. Jacobsen, Science, 2003, 299, 1691. (b) H. Schiff, Ann. Suppl.,
1864, 3, 343.

2.

B. Lippert, Coord. Chem. Rev. 200202 (2000) 487516.

3.

Spectrochimica Acta Part A 79, (2011), 873; Journal of Natural Gas Chemistry 12, (2003),
98 (104); Research Journal of Chemical Sciences Vol. 3(10), 97-99, October (2013)