3.2.

5 Transition metals
The 3d block contains 10 elements, all of which are metals. Unlike the
metals in Groups 1 and 2, the transition metals Ti to Cu form coloured
compounds and compounds where the transition metal exists in
different oxidation states. Some of these metals are familiar as
catalysts. The properties of these elements are studied in this section
with opportunities for a wide range of practical investigations.
Prior knowledge:

• AS Chemistry
• - 3.1.1 – Atomic structure (electron structure).
• - 3.1.7 – Oxidation, reduction and redox reactions
(oxidation states, oxidation, reduction, redox equations).
3.2.5.1 General properties of the transition metals
Learning objective Learning outcome
Give the electron structure of Students should be able to:
transition metals and their
 write the electron structure of
ions.
first row transition metals and
their ions
Know the characteristic
properties of transition  describe what a transition
metals. metal is in terms of electron
structure
Understand the terms  describe the characteristic
complex, ligand co-ordinate properties of transition metals
bond, and co-ordination  define the terms ligand,
number. complex, co-ordinate bond and
co-ordination number.
What is a transition metal?
The d block elements are found in the centre of the periodic
table. As you move across the d block, five d orbitals are filled, up
to a total of ten electrons.

Transition metals are d

block elements that can
form at least one stable
ion with an incomplete d
sub-level.

Transition metals have typical metal properties, such as

conducting heat and electricity, and high melting and boiling
points. They are sonorous, ductile, malleable and lustrous.

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The general properties of transition metals

• Their atoms or ions have an incomplete d sub-shell.

• The form complexes.
• They have variable oxidation states
• The metals and their compounds show catalytic
activity.
• They form coloured ions.
 WHAT ARE TRANSITION METALS?

Transition metals are metals that contain an

incomplete d sub shell in atoms or ions.

Top row transition metals: Sc – Cu

Zn is not a transition metal (Zn & Zn 2+)

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 PROPERTIES OF TRANSITION METALS?

1) They form coloured ions.

photo by Ian Geldard

 PROPERTIES OF TRANSITION METALS?

2) They form complexes (ligands form co-ordinate bonds to the

metal ion).

[Cu(H2O)6]2+ [CuCl4]2-

OH2 2+ Cl 2-
H2O OH2
H2O
Cu
OH2
Cu
Cl
Cl
OH2 Cl

© www.chemsheets.co.uk A2 1028 1-Jun-2016

 PROPERTIES OF TRANSITION METALS?

3) They exhibit variable

oxidation states.
 PROPERTIES OF TRANSITION METALS?

4) They show catalytic activity.

e.g. Ni margarine production

V2O5 making SO3 for H2SO4
Fe Haber process to make NH3
Pt, Pd catalytic converters

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Electron configurations

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 ELECTRON STRUCTURES
This diagram helps you to work out the order in which orbitals fill:
1s 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, …..

2s 2p However, it can be easier to read across the periodic table, but remember
that the first transition metal row is 3d:
3s 3p 3d

4s 4p 4d 4f
1s 1s
4s fills and empties
5s 5p 5d 5f 2s 2p before 3d
6s 6p 6d 3s 3p

4s 3d 4p
7s 7p

Fe [Ar] 4s2 3d6 Cu [Ar] 4s1 3d10

Fe3+ [Ar] 3d5 Cu+ [Ar] 3d10
Sc [Ar] 4s2 3d1 Cu2+ [Ar] 3d9
Sc3+ [Ar] Zn [Ar] 4s2 3d10
V [Ar] 4s2 3d3 Zn2+ [Ar] 3d10
V2+ [Ar] 3d3 Cr [Ar] 4s1 3d5

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Evidence of electronic structure
Successive ionization energies can be used to determine
the electronic structure of an element.

In a transition metal,
electrons are initially
removed from the 4s
sub-level and then the 3d
sub-level. There is only a
small energy difference
between these sub-levels.

When both sub-levels are

empty, the 4s sub-level is
slightly lower in energy and
is filled first.

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Successive ionization energies

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Transition metal electronic structures
When transition metals form ions, the 4s electrons are
removed before the 3d electrons. This means that nearly all
of them make stable 2+ ions.

Ti 1s22s22p63s23p63d24s2
Ti2+ 1s22s22p63s23p63d24s0

Which Period 4 transition metals are likely to make

stable 1+ ions?

Chromium and copper because they lose the one electron

from their 4s sub-level.

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d-block elements or transition metals?
A d block element has its highest energy electron in its d sub-
level. A transition metal is a d block element which has a
partially filled d sub-level in at least one stable ion.

Scandium makes a stable Zinc makes a stable Zn2+ ion

Sc3+ ion with an electronic with an electronic
configuration of [Ar] 3d0 4s0 configuration of [Ar] 3d10 4s0
and is therefore not a and is therefore not a
transition metal. transition metal.

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d block elements vs transition metals

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3.2.5.2 Substitution reactions
Learning objective Learning outcome
Understand the different types of
ligands. Students should be able to:
• explain the difference between, and
Understand ligand exchange. give examples of monodentate,
bidentate and multidentate ligands
Know about oxygen transfer by • explain what happens in a ligand
haemoglobin. substitution (exchange) reaction and
why there may be a change in co-
Understand the chelate effect. ordination number
• describe what haem is, how oxygen is
carried in blood and why carbon
monoxide is toxic
• describe and explain the chelate effect
in terms of enthalpy and entropy
changes.
The formation of complex ions
Transition metals form complex ions
A complex is a central metal atom or ion surrounded by ligands.
A ligand is an ion or molecule which can donate a pair of
electrons to a central metal ion. Ligands are Lewis bases and
nucleophiles.

Ligands are classified by the number of

coordinate bonds (dative covalent)
that they can make.
Water molecules frequently act as
ligands. Each water molecule makes The lone pair of electrons on
a single bond with the metal ion. the oxygen can be donated
Ligands which form single coordinate into the partially filled d sub-
bonds are called unidentate or level of the transition metal.
monodentate.
 COMPLEX FORMATION

Ligand particle with a lone pair that forms co-ordinate

bond to metal

Complex metal ion with ligands co-ordinately bonded to it

Co-ordination number of co-ordinate bonds from ligand(s) to

number metal ions

Lewis base lone pair donor (ligands are Lewis bases)

Lewis acid lone pair acceptor

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 Hexaaqua ions
When transition metal ions dissolve in water they form complex
ions such as [M(H2O)6]n+
i.e. [Cu(H2O)6]2+ , [Ni(H2O)6]2+ , [Fe(H2O)6]3+

e.g.[Cu(H2O)6]2+
Hexaaqua ion - as
there are six water OH2 2+
ligands
co-ordinately H2O OH2
bonded to the Cu
metal ion. H2O OH2
OH2
 Writing complexes
• We write the complexes with the
metal atom or ion and the ligands
inside the square bracket and the
charge is placed outside as a
superscript.
 Coordination number
is the number of coordinate bonds to the metal atom or ion

• Some ligands form more than one coordinate bond to the

metal atom or ion at the centre of the complex.
Q6a. Chem 5
Jan05
 Ligands

• Monodentate (uni)
• Bidentate
• multidentate
monodentate ligands

Monodentate ligands – form one coordinate bond to a

metal atom or ion – they will donate only 1 pair of
electrons.
_ _ _
e.g. H2O:, :OH, :NH3, :CN, :Cl

[Cu(H2O)6]2+ [CuCl4]2-

OH2 2+ Cl 2-
H2O OH2
H2O
Cu
OH2
Cu
Cl
Cl
OH2 Cl
Ligand substitution reactions
• A ligand substitution reaction is one in which one ligand is
coordinately bonded to a metals atom or ion in a complex is
replaced by another ligand.

1. ligand substitution with no change in coordination number

[Co(H2O)6]2+ + 6NH3 ⇌ [Co(NH3)6]2+ + 6H2O

In this reaction both ligands are similar size and both are uncharged.

[Cu(H2O)6]2+ + 4NH3 ⇌ [Cu(H2O)2(NH3)4]2+ + 4H2O

In this reaction four water ligands are replaced – the substitution is
incomplete. However, there is no change in coordination number or charge.
• In the following reactions there is no change in coordination number
or charge.

• 1,2-diaminoethane is a bidentate ligand and only 3 ligands are

required.
2. ligand substitution reaction with change in the coordination
number

[Co(H2O)6]2+ + 4Cl- ⇌ [CoCl4]2- + 6H2O

This is a reaction with Co(II) ions and concentrated HCl.

Cl- is the ligand and is much larger than ammonia or water and
only 4 Cl- can fit around the metal ion.
The coordination number of the complex changes from 6 to 4.

[Cu(H2O)6]2+ + 4Cl- ⇌ [CuCl4]2- + 6H2O (substitution)

Bidentate ligands
Bidentate ligands form two co-ordinate bonds – as they
contain two atoms that donate pairs of electrons to form
coordinate bonds. For example:
Ethane-1,2-diamine (en)
Both nitrogen atoms
donate lone pairs to the
metal ion.

Ethanedioate ion
The two single-bonded
oxygen atoms both
donate lone pairs to the
metal ion.
Bidentate ligands – form two co-ordinate bonds

1,2-diaminoethane ethanedioate O O
CH2 CH2 (C2O42-) C C
H2N NH2 - -
O O

e.g. [Cr(NH2CH2CH2NH2)3]3+ e.g. [Cr(C2O4)3]3-

O
NH2 O C
3+ C O 3-
H2N NH2 O O C O
Cr Cr
H2N NH2 O O C O
NH2 C NH
O 2
O C
O
Other examples - bidentate
Multidentate ligands
Multidentate ligands form several coordinate bonds.

The EDTA4– ion forms six EDTA is abbreviation for

coordinate bonds with a ethylenediaminetetraacetic acid.
metal ion.

Lone pairs are donated

by the four negatively-
charged oxygen atoms
and the two nitrogen
atoms.
Q4 Chem 5Jun10
Bonding atoms in ligands

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Identifying ligands

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Coordination number
The coordination number is the number of coordinate
bonds to the metal ion. This is different to the oxidation state
of the metal ion or complex.

Hexaaquacopper(II) Tetrachlorocobalt(II)
Coordination number = 6 Coordination number = 4

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What is a complex?

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Identify the complex ion

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Chelate effect
LO: describe and explain the chelate effect in terms of enthalpy and entropy
changes.

• All multidentate ligands form complexes called chelates. (“chel”

= crab like).
• Multidentate ligands bind more tightly because of the chelate
effect.
• The metal atom or ions is surrounded by the chelating ligand
such as EDTA4-.

Simplified form of [CoEDTA]2-

complex. A chelate as the Co2+ is
surrounded by EDTA4-. Overall charge
is 2- as Co is 2+ and EDTA is 4-.
White circles represent N and green
represent O- in COO-.
Enthalpy and entropy considerations

[Cr(H2O)6]3+ + 3C2O42- → [Cr(C2O4)3]3- + 6 H2O

4 particles → 7 particles

[Cr(H2O)6]3+ + EDTA4- → [Cr(EDTA)]- + 6 H2O

2 particles → 7 particles

• H negligible (similar number and type of bonds broken/formed)

• S +ve (big increase in entropy).
•  reaction has large –ve G  feasible
• Task 3 Chemsheets

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 CHELATE EFFECT

• When replace ligands with those that form more co-ordinate

bonds reaction is feasible (driven by increase in entropy)
• Reverse reaction is NOT feasible due to large–ve G caused by
big decrease in entropy

chela (latin) = claw / pincer

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20-Jul-12
 CHELATE EFFECT
-
:OOC CH2 CH2 COO:-

:N CH2 CH2 N:
-
:OOC CH2 CH2 COO:-

EDTA4- is an example of a chelating

agent used to prevent poisoning by
metal ions (e.g. Pb2+)
Predicting ligand substitution

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Charge and oxidation number
The overall charge of a complex depends on the oxidation number of the
metal and the number and charge of the ligands.

H2O and NH3 are neutral ligands, the overall charge of the complex is
same as the oxidation number of the metal.
[Fe(H2O)6]3+ oxidation number Fe = +3
[Cu(H2O)6]2+ oxidation number Cu = +2
[Co(NH3)6]2+ oxidation number Co = +2

With anionic ligands, the negative charge of the ligand contributes to the
overall charge of the complex ion.
[CuCl4]2- oxidation number of Cu is +2, four Cl- ligands contribute charge
of -1 each, total is -4; overall +2 -4 = -2.

[Fe(H2O)5SCN]2+ oxidation number of Fe is +3, water ligands are neutral,

SCN has charge -1; overall charge is +2.
 Haem and haemoglobin
LO: describe what haem is, how oxygen is carried in blood and why carbon
monoxide is toxic

Haemoglobin is the molecule that causes blood to appear red. It

carries oxygen from the lungs to cells in the body.
Haemoglobin contains an Fe2+ ion
which forms a haem complex.
• The Fe(II) can accept 6 pairs of
electrons from ligands.
• The porphyrin ring (tetradentate
ligand) contains 4 N atoms and
forms 4 coordinate bonds with
Fe(II).
It also binds to a unidentate globin
molecule. One coordination site is left
that can bind loosely to an oxygen
molecule.
 COMPLEX FORMATION

Multidentate ligands – form several co-ordinate bonds

porphyrin e.g. haem

• Oxygen is a poor ligand that is easily released to cells, where its
concentration is low. Ligands that can form stronger bonds with the
Fe2+ ion, such as carbon monoxide, bind irreversibly and destroy
haemoglobin’s ability to carry oxygen. These substances are toxic.

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