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3.2.5 Complex formation 20/01/2024

Objectives:

To define the terms ligand, co-ordinate bond & coordination number

To explain what is meant by unidentate, bidentate & multidentate

RE-CAP Key words:

Write down 3 general properties of transition Ligand

elements Coordination no.
Unidentate
Bidentate
Multidentate
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3.2.5 Complex formation 20/01/2024

Sharing is caring

You each have one definition of a key word relating to this lesson
Share your definitions with others to complete the glossary table below

Key Word Definition

Complex Ion
Coordinate Bond
Coordination Number
Ligand
Unidentate

Bidentate

Multidentate
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3.2.5 Complex formation 20/01/2024

Key Word Definition

Complex Ion Metal ion surrounded by co-ordinately bonded ligands

Coordinate Bond A covalent bond in which both electrons in the shared pair come
from the same atom
Coordination Number The number of coordinate bonds to ligands that surround a transition
metal ion
Ligand An ion or molecule that forms a coordinate bond with a transition
metal
Unidentate Ligand that can only form one coordinate bond

Bidentate Ligand that can form two coordinate bonds

Multidentate Ligands that can form more than one coordinate bond
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3.2.5 Complex formation 20/01/2024

COMPLEXES

•Complexes are formed when transition metals or their ions form co-ordinate (dative) bonds
with ligands

•A complex ion is an ion comprising of one or more ligands attached to a central metal
cation by means of a dative covalent bond
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Ligands 20/01/2024

A ligand is a species which can use its lone pair of electrons on one of its atoms to form a dative
covalent bond with a transition metal

Examples of ligands are:

•H2O
•NH3
•Cl-
•OH-
•CN-
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3.2.5 Complex formation 20/01/2024

Co-ordinate bond

A co-ordinate bond (dative covalent bond) is a covalent bond in which both electrons come from the
same atom

In the case of
complex ions, the
co-ordinate bonds
are formed by the
overlap of an orbital
containing a lone
pair of electrons
with a vacant orbital
on the transition
metal
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3.2.5 Complex formation 20/01/2024

Co-ordination number

The number of lone pairs of electrons which a cation can accept is known as the coordination
number of the cation

It depends on the size and electronic configuration of that cation, and also on the size and
charge of the ligand

Coordination number 6 is the most common, although 4 and 2 are also known
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3.2.5 Complex formation 20/01/2024

Lewis acid / Base

This will be useful later in the unit

Lewis Acid
In complexes: → electron
pair acceptor
•The metal ion acts as a Lewis Acid
•Accepts lone pairs of electrons Lewis Base
→ electron
•The ligand acts as a Lewis Base pair donor
•Donates lone pairs of electrons
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Example

An example of a complex ion is:

[Cu(H2O)6]2+

Note that the formula of

the ion is always written
inside square brackets
H 2O
The overall charge is written H 2O OH2
outside the brackets Cu 2+
H 2O OH2
OH2
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3.2.5 Complex formation 20/01/2024

Objectives:

To explain how the size of ligand affects the shape of a complex ion
To explain how ligand charge affects complex ion charge

Starter: Key words:

What do you think ‘dentate’ might mean? Monodentate

Multidentate
Why is it used in complex ion formation?
Bidentate
Chelate
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3.2.5 Complex formation 20/01/2024

Monodentate Ligands

•Meaning ‘single toothed’ → form 1 co-ordinate bond

•Common monodentate ligands are H2O, Cl-, NH3 and CN-

•Can be negatively charged ions or neutral molecules

Ammonia only has 1 pair of

electrons to donate
Water has 2 lone pairs. BUT they
are so close together it can only
form one coordinate bond at a
time!
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3.2.5 Complex formation 20/01/2024

BIDENTATE LIGANDS
• Ligands that can form two co-ordinate bonds since they donate two lone pairs of electrons (from two donor
atoms)
• Examples:
• Ethane-1,2-diamine
(NH2CH2CH2NH2) Each ethane-1,2-diamine molecule forms 2 coordinate
bonds with the metal ion

NH2CH2CH2NH2

2 amine groups. Each has a lone

pair of electrons to donate
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3.2.5 Complex formation 20/01/2024

Multidentate ligands

Can form three or more co-ordinate bonds by donating at least three lone pairs of electrons
to the metal ion

Extremely stable since the reaction results in an increase in entropy

EDTA is a common example

Ethylenediaminetetraacetate

How many coordinate bonds can it form?

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Ethylenediaminetetraacetate 20/01/2024

EDTA4- has six lone pairs (two on

nitrogen atoms and 4 on oxygen
atoms)
It can form six coordinate bonds
with a metal ion

Complex ions with multidentate

ligands are called chelates (‘key-
lates) from the Greek word for claw
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Multidentate ligands 20/01/2024

[Cu(H2O)6]2+ + EDTA ➔ [Cu(EDTA)]2- + 6H 2O

They can be used to remove metal ions from solution

The six water ligands are replaced by one EDTA ligand

This results in an increase in the number of particles in solution

Hence an increase in entropy

(more particles = more disorder = higher entropy)

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The Chelate Effect 20/01/2024

Monodentate Ligands
Increasing strength of
Bidentate Ligands binding in a complex
Multidentate Ligands
Multidentate ligands bind to a complex much more tightly than a Monodentate ligand. One way of looking at it is if you
are holding something with two hands rather than one, you are not as likely to drop it. (Three hands would be even
better!) This is known as the Chelate effect.

The chemical reasons for the chelate effect involve relative enthalpy and entropy changes upon binding a multidentate
ligand. In terms of enthalpy, in order to completely remove a bidentate ligand, two coordinate bonds must be broken. That
costs more energy than breaking one coordinate bond for a monodentate ligand.

In terms of entropy, which deals with the distribution of energy within a system, it is generally thought that bringing two
molecules together (a bidentate ligand and a metal complex) costs less than bringing three molecules together (two
monodentate ligands and a metal complex). That's because individual molecules are free to move around, tumble and
vibrate independently. Once they come together, they have to do all these things together. Since these different types of
motion represent different ways of distributing energy, if the system becomes more restricted, energy can't be distributed
in as many states.
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Types of ligand 20/01/2024

The charge on the ligand and the oxidation state of the metal determines the overall charge of the complex

Neutral ligands result in positively charged complexes, where the overall charge of the complex equals the oxidation state
of the metal ion

Negatively charged ligands result in a negatively charged complex

Oxidation states

Overall charge on a complex ion is its total oxidation state

It’s put outside the brackets

You can work out the oxidation state of the metal ion by:

Oxidation state of = Total oxidation state - Sum of oxidation

metal ion of complex states of ligands
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Oxidation states
Back to this example:

[Cu(H2O)6]2+

Overall = 2+
H2O ligands = Charge = 0

Cu2+ ion has an H 2O

oxidation state of +2
H 2O OH2
Cu2+ ion has a co-ordination Cu 2+
number of 6 H 2O OH2
OH2
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Questions

Work out the oxidation states (OS) and co-ordination numbers

(CN) of the following complexes:

[Cu(H2O)6]2+ OS: +2 CN:6

[Ag(NH3)2]+ OS: +1 CN:2
[Cu(NH3)4]2+ OS: +2 CN:4
[Cu(Cl)4]2- OS: +2 CN:4
[Fe(CN)6]3- OS: +3 CN:6
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Shapes of complexes 20/01/2024

The co-ordination number dictates the shape of the complex

This is the number of coordinate bonds formed with the central metal ion

2 co-ordinate = linear

4 co-ordinate = tetrahedral Bond angles?

6 co-ordinate = octahedral
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Shapes of complexes 20/01/2024

Six coordinate bonds

Octahedral shape

6 points BUT 8 faces

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Four Coordinate bonds

•Usually have a tetrahedral shape

•A few complexes have a square planar shape

Cisplatin
(Pt(NH3)2Cl2) is
an example
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Two coordinate bonds

• Most have a linear shape

• E.g. [Ag(NH3)2]+

•A solution of this is called Tollens’ reagent which is used to tell aldehydes from ketones.
Aldehydes reduce it to silver, while ketones do not
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Useful applications of EDTA

EDTA has many uses, for example:

An antidote in metal poisoning. It removes poisonous metal ions (e.g. mercury and lead)
from the bloodstream

It is an anticoagulant, so is used in blood transfusions to remove calcium ions which cause

blood clotting, and in the storage and analysis of blood in forensic science

To remove calcium ions from hard water. For this reason many cleaning products contain it,
such as shampoos, shower gel etc
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20/01/2024

O. J. Simpson

Former American football star and actor O. J. Simpson was tried on two counts of
murder following the June 1994 deaths of his ex-wife and her friend

Simpson was acquitted after a lengthy trial that lasted over nine months

He was probably guilty, but the LAPD planted a piece of evidence to try to secure a
guilty verdict ... But EDTA was present!!!
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Shapes of complexes 20/01/2024

Blood and DNA evidence was found at the crime scene that suggested Simpson was guilty

Clothing belonging to the ex-wife with her blood on it was found at Simpson's house

Had previously been charged with assault on his ex-wife

There was a left-handed glove at the crime scene with blood from all 3 people

The right-handed matching glove was found at Simpson’s house

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•However, some of the blood samples were found to contain EDTA

•This had been added after it was taken from Simpson to prevent it from coagulating

•A detective from the LAPD (the most corrupt police force in the world) planted the blood on
the evidence in an attempt to secure a guilty verdict

•Simpson was acquitted

•The guilty detective “pleaded the fifth” in court when quizzed on planting the evidence

•Refused to answer a question because the response could provide self-incriminating

evidence of an illegal act
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Haemoglobin 20/01/2024

Blood naturally contains a multidentate ligand called haemoglobin

The haemoglobin molecule contains
4 nitrogen atoms that are
co-ordinately bonded to iron
Two more co-ordinate bonds
are formed to the iron, one
from the nitrogen atom in the
protein globin and the other
from the oxygen in a molecule
of oxygen (oxyhaemoglobin) or
from a water molecule
(deoxyhaemoglobin)
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Haemoglobin 20/01/2024

This complex transports the oxygen in our blood

around our bodies, due to the weak co-ordinate bonds
formed in the iron complex

Carbon monoxide can also form co-ordinate bonds

with the complex and the bond is more stable than the
bond formed with oxygen. Therefore if carbon
monoxide is breathed in and concentration is high
enough, it can cause oxygen starvation to the body and
is life threatening
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CISPLATIN

One of the most-successful anti-caner drugs

developed in recent years is cisplatin

It is believed to work by bonding to DNA so that it

prevents the replication of cancerous cells

Its isomer transplatin has no anti-cancer

properties
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How it works 20/01/2024

Bonds between guanine on separate strands of DNA are coordinate ones with nitrogen
These displace the two ammonia molecules from cisplatin
the platinum atom is now binded to DNA bases
This prevents DNA from unravelling – which it needs to do in order for replication (cancer is
uncontrollable cell replication
The damaged DNA elicits DNA repair mechanisms, which in turn activate apoptosis (cell
death) when repair proves impossible.

Pt(NH3)2Cl2 + H2O → [Pt(NH3)2Cl(H2O)]+ + Cl–

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I CAN… I AM…
Define the terms ligand, co-ordinate bond and co- C
ordination number
Explain what unidentate, bidentate and multidentate B
ligands are

Calculate co-ordination numbers and oxidation states and A

shapes of complex ions
Give examples of each type of ligand and analyse some of A*
their applications

How low can you go?? Write what you can do and what grade this is
→ show some proof you can do this!
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Naming compounds
•The name contains:
a) The ligand
b) The number of ligands
c) The oxidation state of the transition metal ion

Ligand Name in Complex Formula Charge

Water aqua H2O 0
Chloride chloro Cl- -1
Ammonia amine NH3 0
Cyanide cyano CN- -1
Hydroxide Hydroxo OH- -1
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Naming complexes

•The number of ligands has a prefix

Number of ligands Prefix

2 di
4 tetra
6 hexa

•If more than one ligand is present, they are named alphabetically – ignoring the prefix
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Naming complexes

When a complex is cationic the name of the metal is as you would expect it

When a complex is an Metal Name in anionic

anionic, the metal name
ends in “ate” Cobalt Cobaltate
Chromium Chromate
The oxidation state of Vanadium Vanadate
the metal is given in
roman numerals. Copper Cuprate
Iron Ferrate
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Questions

•Work out the name of the following complexes:

[Cu(H2O)6]2+ hexaaquacopper (II)

[Co(Cl)4]2- tetrachlorocobaltate(II)
[Cr(NH3)6]2+ hexaaminechromium(II)
[Ag(NH3)2]+ diaminesilver(I)
[Co(H2O)6]2+ hexaaquacobalt(II)
[Cu(Cl)4]2- tetrachlorocuprate(II)
[Ag(Cl)2]- dichloroargentate(I)