Complex formation

complex :is a central metal ion surrounded by ligands.

ligand.: An atom, ion or molecule which can donate a lone electron pair.

2+
OH2
H2O OH2
Cu
H2O OH2
OH2

Co-ordinate bonding is involved in complex formation.

Co-ordinate bonding is when the shared pair of electrons in the covalent bond come from only one of the
bonding atoms.
Co-ordination number: The number of co-ordinate bonds formed to a central metal ion.

Ligands can be unidentate (e.g. H2O, NH3 and Cl- ) which can form one coordinate bond per ligand or
bidentate (e.g. NH2CH2CH2NH2 and ethanedioate ion C2O4 2- ) which have two atoms with lone pairs and
can form two coordinate bonds per ligand
or multidentate (e.g. EDTA4- which can form six coordinate bonds per ligand).

Bidentate ligands contain two donor atoms. They bond to the metal ion through two atoms.

- -

:
:

O O
:

H N CH2 CH2 N H
C C
H H
O O
1,2-diaminoethane NH2CH2CH2NH2 -
Ethanedioate(oxalate) ion
-OOC-COO-

3+
A complex with bidentate
CH2
NH2
ligands e.g. O
H2 C [Cr(NH2CH2CH2NH2)3]3+ C 3-
NH2 CH2 O
NH2 C O

Cr There are 3 bidentate O

CH2 O O A complex with
NH2 NH2 C
ligands in this complex Cr
C bidentate ethanedioate
NH2 each bonding in twice
H2 C O O O ligands e.g. [Cr(C2O4)3]3-
CH2 to the metal ion.
O C O
C
O
It has a coordination number of 6

Equations to show formation of bidentate and mutidentate complexes

[Cu(H2O)6]2+ + 3NH2CH2CH2NH2  [Cu(NH2CH2CH2NH2)3]2+ + 6H2O
[Cu(H2O)6]2+ + 3C2O42- [Cu(C2O4)3]4- + 6H2O

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 O
The EDTA4- anion has the formula
O O C
-O C CH2 CH2 C O- O
N CH2 CH2 N
O CH2
-O C CH2 CH2 C O-
C CH2
O O
O N
with six donor sites(4O and 2N) and forms a 1:1 CH2
complex with metal(II) ions Cu
O CH2
As it can form six dative covalent bonds with the N
metal ion, edta will only ever have a ratio of one
molecule of edta to one ion of the metal. C CH2
eg [ Ni(edta)]2-
O
O CH2
[Cu(H2O)6]2+ + EDTA4- [Cu(EDTA)]2- + 6H2O C

The stability of the EDTA complexes has many applications. It can be added to rivers to remove
poisonous heavy metal ions as the EDTA complexes are not toxic. It is in many shampoos to remove
calcium ions present in hard water, so helping lathering.

Quantitative calculations with complex ions

EDTA titrations
The formation of the stable EDTA complex with metal ions can with the choice of suitable indicator be
done in a quantitative titration.
[Cu(H2O)6]2+ + EDTA4-  [Cu(EDTA)]2- + 6H2O Always the same 1:1 ratio with any metal ion

A river was polluted with copper(II) Step1 : find moles of KMnO4

ions. 25.0 cm3 sample of the river moles = conc x vol = 0.0150 x 6.45/1000
water was titrated with a 0.0150 = 9.68x10-5 mol
mol dm–3 solution of EDTA4– , 6.45
Step 2 : using balanced equation find moles Cu2+
cm3 were required for complete
reaction. 1:1 ratio
Calculate the concentration, in mol = 9.68x10-5 mol
dm–3, of copper(II) ions in the river Step 3 : find conc Cu2+ in 25cm3
water. = 9.68x10-5 /0.025
= 0.00387 moldm-3

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 H2C Haem is an iron(II) complex
with a multidentate ligand.

CH3
H3C

N
N
CH2
Fe
N N
H3C Fe(II) in haemoglobin enables oxygen to be transported
in the blood. Haem is an iron(II) complex with a
CH3 multidentate ligand.

CO is toxic to humans as CO can from a strong

coordinate bond with haemoglobin. This is a stronger
bond than that made with oxygen and so it prevents the
oxygen attaching to the haemoglobin.
COOH
COOH

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Shapes of complex ions
NH3
Octahedral

Transition metal ions commonly

form octahedral complexes with
small ligands (e.g. H2O and NH3).
NH3
2+ NH3
NH3
Co3+
H3 N NH3 NH3
Ni
H3 N NH3 NH3
NH3

NH3

Tetrahedral
NH3
Transition metal ions commonly form tetrahedral
complexes with larger ligands (e.g.Cl- ).

Cl 2-
Zn2+
NH3
Cu
NH3
Cl Cl
NH3
Cl

Square planar

NH3
square planar H 3N Cl
complexes are also Pt NH3
formed, e.g. cisplatin Pt2+
H 3N Cl NH3

NH3

Linear

Ag+ commonly forms linear complexes

e.g. [Ag(NH3)2]+, [Ag(S2O3)2]3- and NH3 Ag+ NH3
[Ag(CN)2]- (all colourless).
+
H3 N Ag NH3

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Isomerism in complex ions

Complexes can show two types of stereoisomerism: cis-trans isomerism and optical isomerism

Cis-trans isomerism

H3N NH 3 H3N Cl
Ni Ni
Cl Cl Cl NH 3
Cis-Ni(NH3)2Cl2 trans-Ni(NH3)2Cl2

NH3 +
NH3 +
Cl NH3 Cl NH3
Cr
Cl Cr
NH3 NH3
Cl
NH3 NH3

trans-[CoCl2(NH3)4]+
Cis-[CoCl2(NH3)4]+

Complexes with 3 bidentate ligands can form two optical

Optical isomerism isomers (non-superimposable mirror images).

2+
2+
CH2 CH2
NH2 H2N CH2
H2 C
NH NH2 CH H2C NH2 NH2
2 -
Ni Ni
CH2 H2C NH2 NH2
NH NH2

NH2 NH2 CH
H2 C 2
CH2 CH2

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Cisplatin
- -
The Pt(II) complex cisplatin is used as an anticancer drug. H3N Cl Cl NH3
2+ 2+
Pt Pt
The cisplatin version only works as two chloride ions are displaced H3N - H3N -
Cl Cl
and the molecule joins on to the DNA. In doing this it stops the
replication of cancerous cells. cisplatin transplatin

Cisplatin prevents DNA replication in cancer cells by a ligand

replacement reaction with DNA in which a dative covalent bond
is formed between platinum and a nitrogen atom on guanine

NH3
Pt O
NH3
N
NH

NH N NH 2
The N and O atoms marked in red can’t
bond to cis-platin as they are involved in the
bonding within the DNA

Cisplatin can also prevent the replication of healthy cells

by bonding on to healthy DNA which may lead to
unwanted side effects like hair loss. Society needs to
assess the balance between the benefits and the adverse
effects of drugs, such as the anticancer drug cisplatin.

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Stability of complexes
The substitution of monodentate ligand with a bidentate or a multidentate ligand leads to a more stable complex. This is
called the chelate effect

This chelate effect can be explained in terms of a positive entropy change in these reactions as more molecules
of products than reactants

[Cu(H2O)6]2+ (aq) + EDTA4- (aq)  [Cu (EDTA)]2- (aq) + 6H2O (l)

The copper complex ion has changed from having unidentate ligands to a multidentate ligand.
In this reaction there is an increase in the entropy because there are more moles of products than reactants
(from 2 to 7), creating more disorder.

The enthalpy change is small as there are similar numbers of bonds in both complexes.

Free energy ΔG will be negative as ΔS is positive and ΔH is small.

The stability of the EDTA complexes has many applications. It can be added to rivers to remove poisonous heavy
metal ions as the EDTA complexes are not toxic. It is in many shampoos to remove calcium ions present in hard
water, so helping lathering.

[Co(NH3)6]2+ + 3NH2CH2CH2NH2  [Co(NH2CH2CH2NH2)3]2+ + 6NH3

This reaction has an increase in entropy because of the increase in moles from 4 to 7 in the reaction. ΔS is
positive.
Its enthalpy change ΔH is close to zero as the number of dative covalent and type (N to metal coordinate
bond) are the same so the energy required to break and make bonds will be the same.
Therefore Free energy ΔG will be negative and the complex formed is stable.

Stability constants Kstab

A ligand exchange reaction is considered as equilibria then

[Cu(H2O)6]2+ + 4Cl- ⇌ [CuCl4]2- + 6H2O
an equilibrium expression can be written

[CuCl42- aq] .
H2O is not included in the expression because it is concentration is
Kstab = assumed to be constant.
[Cu(H2O)6 aq2+] [Cl- aq]4
The value of K is called the stability constant for complex ions. The
larger the stability constant the more stable the complex ion.

[MX64- aq]
M2+(aq) + 6X– (aq) MX6 4– (aq) Kstab =
[M 2+aq] [X- aq]6

The value of Kstab is called the stability constant for complex ions. The
larger the stability constant the more stable the complex ion. Ligand Log Kstab
Cl- 5.62
A complex ion with a small stability constant will not displace the
ligand from a more stable complex ion with a larger stability constant. NH3 13.1
eg adding ammonia to a complex ion of copper and edta will not result
in a colour change Edta4- 18.8

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More on some common ligands
O

Ethanedioate C2O42- C 3-
O O A 6 coordination number
C
complex with bidentate
O
O O
C ethanedioate ligands e.g.
[Cu(H2O)6]2+ + 3C2O42- [Cu(C2O4)3]4- + 6H2O Cr [Cr(C2O4)3]3-
C
O O O

[Cr(H2O)6]3+ + 3C2O42- [Cr(C2O4)3]3- + 6H2O O C O Octahedral shape with

C 90o bond angles
O

Partial substitution of ethanedioate ions may 2-

occur when a dilute aqueous solution containing OH2
ethanedioate ions is added to a solution O O O O
C
containing aqueous copper(II) ions. In this C
Cu
reaction four water molecules are replaced and C C
O O O O
a new complex is formed.
OH2
[Cu(H2O)6]2+ + 2C2O42- [Cu(C2O4)2(H2O)2]2- + 4H2O

Ethane-1-2-diamine
Ethane-1-2-diamine is a common bidentate ligand.
There are 3 bidentate ligands in this
[Cu(H2O)6]2+ + 3NH2CH2CH2NH2  [Cu(NH2CH2CH2NH2)3]2+ + 6H2O complex each bonding in twice to the
metal ion
CH2 3+
[Co(NH3)6]2+ + 3NH2CH2CH2NH2  [Co(NH2CH2CH2NH2)3]2+ + 6NH3 H2 C
NH2

This reaction has an increase in entropy because of in the increase NH2 NH2 CH2
in moles from 4 to 7 in the reaction. ΔS is positive. Cr
CH2
NH2 NH2
Its enthalpy change ΔH is close to zero as the number of dative
covalent and type (N to metal coordinate bond) are the same so NH2
H2 C
the energy required to break and make bonds will be the same. CH2
Therefore Free energy ΔG will be negative and the complex
formed is stable. It has a coordination number of 6
Octahedral shape
Bond angle around Cr 90o

Ethane-1-2-diamine, as a base, can also carry out the deprotonation reactions

(similar to those of ammonia) forming hydroxide precipitates.
2[Al(H2O)6]3+ (aq) + 3 H2NCH2CH2NH2 (aq)  2Al(H2O)3(OH)3 (s) + 3 [H3NCH2CH2NH3 ]2+ (aq)

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 Using Silver nitrate to work out formulae of chloride containing complexes

Sometimes a compound containing a complex may have Cl- ions acting as ligands inside the complex and
Cl- ions outside the complex attracted ionically to it. If silver nitrate is added to such a compound it will only
form the silver chloride precipitate with the free chloride ions outside of the complex.

e.g. Co(NH3)6Cl3 reacts on a 1:3
mole ratio with silver nitrate as
there are three free Cl- ions. So
all 3 Cls are outside the complex.
e.g. Cr(NH3)5Cl3 reacts on a 1:2
mole ratio with silver nitrate as
there are two free Cl- ions. So 1
Cl is a ligand and 2 are outside
the complex.
e.g. Cr(NH3)4Cl3 reacts on a
1:1 mole ratio with silver
nitrate as there is one free Cl-
ion. So 2 Cl’s are ligands and
1 is outside the complex.

NH3
3+ +
H3N NH3 - NH3
2+ NH3
Co 3Cl H3N NH3 -
H3N NH3 -
Cr Cl
H3N NH3 Cr 2Cl -
- H3N Cl
NH3 H3N Cl -
Cl
NH3

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