Transition Metals

1
 Vocabulary

• Transition metals, characteristics, complex

ion, ligands
• to predict the shape, octahedral, tetrahedral,
linear
• variable oxidation states
• general mechanism, catalysis

2
 Learning Objectives
• understand what is meant by a transition metal and be able to describe this in terms of
electronic structure (Ti - Cu)
• recognise the characteristics of transition metal chemistry
• understand the general structure of a complex ion and the nature of ligands
• know that ligands can be unidentate or multidentate and be able to identify examples of
each
• understand, be able to predict the shape of, and be able to draw octahedral, tetrahedral
and linear complexes
• understand the reasons for the colours and colour changes which complex ions undergo
on reaction and be able to give a general description of this in terms of electronic
transitions
• understand the use of and be able to use spectrometry to determine concentration
• know that transition elements show variable oxidation states and be able to describe
specified examples
• know that transition metals are generally good catalysts and be able to account for this in
terms of variation of oxidation states
• understand a general mechanism for heterogeneous catalysis and know specified
examples
• understand a general mechanism for homogeneous catalysis and know specified examples
• know that haemoglobin contains iron complexes and understand its role in oxygen 3
transport, including carbon monoxide poisoning
 WHAT ARE TRANSITION METALS?

Transition metals are metals that contain an

incomplete d sub shell in atoms or ions.

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Physical Properties of Transition Metals

Transition metals:

 Have high melting points.

 Have high densities.

 Are hard and rigid (construction materials)

 Are good conductors of electricity and heat.

5
Horizontal trends in Atomic radius and
IE1 of the Period 4 elements.

Atomic Radius (pm)

Transition Elements

First Ionization Energies (kJ/mol)

Transition Elements
6
 D-block Elements
 The electronic structures of the 4th period d-block
elements shown are:
Sc [Ar] 4s23d1

Ti [Ar] 4s23d2

V [Ar] 4s23d3

Cr [Ar] 4s13d5

Mn [Ar] 4s23d5

Fe [Ar] 4s23d6

Co [Ar] 4s23d7

Ni [Ar] 4s23d8

Cu [Ar] 4s13d10

Zn [Ar] 4s23d10

 Why are their anomalies for Cu and Cr? 7

 Transition metals
 Not all d block elements count as transition metals!

 A transition metal is one which forms one or more stable

ions which have incompletely filled d orbitals.

 On the basis of this definition, scandium and zinc don't count

as transition metals - even though they are members of the d
block.

 Scandium has the electronic structure [Ar]4s23d1. When it

forms ions, it always loses the 3 outer electrons and ends up
with an argon structure. The Sc3+ ion has no d electrons
and so doesn't meet the definition.

 Zinc has the electronic structure [Ar]4s23d10. When it forms

ions, it always loses the two 4s electrons to give a 2+ ion
with the electronic structure [Ar]3d10. The zinc ion has full d
level and doesn't meet the definition either.
8
 Transition metals
But what about Copper?

 Copper, [Ar]4s13d10, forms two ions. In the Cu+

ion the electronic structure is [Ar]3d10. However,
the more common Cu2+ ion has the structure
[Ar]3d9.

 Copper is definitely a transition metal because

the Cu2+ ion has an incomplete d level.

9
 Transition metal Ions
 When the Periodic Table is being built, the 4s orbital is
filled before the 3d orbitals. This is because in the empty
atom, 4s orbitals have a lower energy than 3d orbitals.

 However, once the electrons are actually in their orbitals,

the energy order changes - and in all the chemistry of
the transition elements, the 4s orbital behaves as the
outermost, highest energy orbital.

Remember:

When d-block elements form ions, the 4s electrons are

lost first.

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 PROPERTIES OF TRANSITION METALS?

1) They exhibit variable oxidation states.

2) They form complexes.
3) They show catalytic activity.
4) They form coloured ions.
 PROPERTIES OF TRANSITION METALS?

1) They exhibit
variable oxidation
states.
 Oxidation States

The most common oxidation states are shown

with the larger circles in this table.

13
 Oxidation States
Transition metals often have more than one common
oxidation state.

 Most have +2 state due to loss of s electrons.

 Oxidation numbers greater than 2 are due to loss of d
electrons as well as s.
 The higher oxidation states are found in complex ions
or compounds with O or F.
 Examples:
 chromate(VI) (dichromate) ion Cr2O72-
 manganate(VII) (permanganate) ion MnO4-

14
 Electron Configurations and
Oxidation States
To write the electronic structure for Co2+:

[Ar] 3d74s2
Co
Co2+ [Ar] 3d7

The 2+ ion is formed by the loss of the two 4s electrons.

To write the electronic structure for V3+:

[Ar] 3d34s2
V
V3+ [Ar] 3d2
The 4s electrons are lost first followed by one of the 3d electrons.
15
 Copper

 In solution exists in +1 or +2 state.

 +1 salts generally white, insoluble.

 +2 salts commonly blue, water-soluble.

16
 Chromium

 Oxidized by HCl or H2SO4 to form blue Cr2+ ion.

 Cr2+ oxidized by O2 in air to form green Cr3+.

 Cr also found in +6 state as in CrO42− and the

strong oxidizer Cr2O72−.

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 PROPERTIES OF TRANSITION METALS?

2) They form complexes.

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

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

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 COMPLEX FORMATION

Ligand an atom, ion or a molecule 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)

number to metal ions

Lewis base lone pair donor (ligands are Lewis bases)

Lewis acid lone pair acceptor

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Complex ions
 A central metal atom bonded to
a group of molecules or ions is
a metal complex.

 If the complex bears a charge,

it is a complex ion.

 The bond is formed

between a Lewis acid and
a Lewis base.
 The ligands (Lewis bases)
have nonbonding electrons.
 The metal (Lewis acid) has
empty orbitals. 20
 Lewis Acid-Base

 In the Lewis theory of acid-base reactions,

bases donate pairs of electrons and acids
accept pairs of electrons.

21
Lewis

22
 Lewis

 One advantage of the Lewis theory is the way it

complements the model of oxidation-reduction
reactions. Oxidation-reduction reactions involve a
transfer of electrons from one atom to another, with
a net change in the oxidation number of one or more
atoms.
 The Lewis theory suggests that acids react with
bases to share a pair of electrons, with no change in
the oxidation numbers of any atoms.
 The principal advantage of the Lewis theory is the
way it expands the number of acids and therefore
the number of acid-base reactions.

23
 Complex ions
 The molecules or ions coordinating to the metal are
the ligands.

 They are usually anions or polar molecules.

 The coordination of the ligand with the metal can

greatly alter its physical properties, such as color, or
chemical properties, such as ease of oxidation.
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 COMPLEX FORMATION

Lewis base lone pair donor (ligands are Lewis bases)

Lewis acid lone pair acceptor

H+ + :OH- → H2O

Lewis Lewis
acid base

Ligands form co-ordinate

bonds via lone pairs
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Bonding in Complex Ions:
Example: [Fe(H2O)6]3+

Iron has the electronic structure:

[Ar]3d64s2

When it forms an Fe3+ ion it loses

Looking at this as electrons-in-
the 4s electrons and one of the 3d
boxes, at the bonding level:
electrons to leave

[Ar]3d5

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Bonding in Complex Ions:
Example: [Fe(H2O)6]3+

• The single electrons in the 3d level are NOT involved in the

bonding in any way.

• Instead, the ion uses 6 orbitals from the 4s, 4p and 4d levels
to accept lone pairs from the water molecules.

• Before they are used, the orbitals are re-organised (hybridized)

to produce 6 orbitals of equal energy.

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Bonding in Complex Ions:
Example: [Fe(H2O)6]3+

• Once the co-ordinate bonds have been formed, this is

what the structure of this complex ion is:

• Because the iron is forming 6 bonds, the co-ordination

number of the iron is 6 (octahedron)

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Bonding in Complex Ions:
Example: [CuCl4]2+

Because chloride ions are bigger than water molecules, you

cannot fit 6 around the central ion - that's why there are 4.

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 COMPLEX FORMATION

Unidentate ligands – form one co-ordinate bond

e.g. H2O:, :OH-, :NH3, :CN-, :Cl-

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

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

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 Polydentate Ligands

 Some ligands have two or

more donor atoms.

 These are called polydentate

ligands.

 In ethylenediamine,
NH2CH2CH2NH2, represented
here as “en”, each N is a
donor atom.

 Therefore, en is bidentate.

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 COMPLEX FORMATION
Bidentate ligands – form two co-ordinate bonds

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

[Cr(en)3]3+ [Cr(C2O4)3]3-
O
O C
NH2 3+ C O 3-
H2N NH2 O O C O
Cr Cr
H2N NH2 O O C O

NH2 C NH2
O C
O
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Polydentate Ligands

Ethylenediaminetetraacetate EDTA,
has six donor atoms.

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 COMPLEX FORMATION

EDTA4-

-
:OOC CH2 CH2 COO:-

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

e.g. [Cu(EDTA)]2-
 COMPLEX FORMATION

porphyrin e.g. haem

 Polydentate Ligands
Hemoglobin
 The functional part of this is an iron(II) ion surrounded by a
molecule called heme.

 This is a sort of hollow ring of carbon and hydrogen atoms,

at the centre of which are 4 nitrogen atoms with lone pairs
on them.

 We could simplify the heme with the trapped iron ion as:

36
 Polydentate Ligands
Hemoglobin
 The iron forms 4 co-ordinate bonds with the heme, but still has
space to form two more, one above and one below the plane of
the ring.

 The protein
globin attaches
to one of these
positions using a
lone pair on one
of the nitrogens in
one of its amino
acids.

 The interesting part is the other position. 37

Carbon monoxide poisoning

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39
 Polydentate Ligands

Hemoglobin and the octahedral complex in heme.

40
Polydentate Ligands

Chlorophyll a is a
tetradentate ligand.

41
 SHAPES OF COMPLEX IONS

Co-ordination
2 4 4 6
number
linear tetrahedral square planar octahedral

Shape M M M
M

Bond angles 180º 109½º 90º 90º

Ag+ Large ligands Pt2+

Occurrence Commonest
complexes (e.g. Cl-) complexes

e.g. [Ag(NH3)2]+ [CuCl4]2- [PtCl4]2- [Cu(H2O)6]2+

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SHAPES OF COMPLEX IONS
SHAPES OF COMPLEX IONS

For each of the following complexes:

• Draw the complex.

• Name the shape.
• Show bond angles.
• Give the metal oxidation state.
• Give the co-ordination number.

1) [Ag(CN)2]- 4) [Co(en)2Cl2 ]+

2) [Cr(NH3)6]3+ 5) [Pt(NH3)2Cl2]

3) [Ni(en)3]2+ 6) [Fe(C 2
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O 4 ) 3 ] 4-
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 SHAPES OF COMPLEX IONS
_
1 Linear
NC Ag CN
180º

Ag +1

Co-ordination number = 2
2 NH3 3+ Octahedral

H3N NH3 90º

Cr
H3N NH3
Cr +3
NH3
Co-ordination number = 6

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 SHAPES OF COMPLEX IONS

NH2 3+
2+ Octahedral
3
H2N NH2
Ni
Cr 90º
H2N NH2
NH2 Ni +2

Co-ordination number = 6
4 + Octahedral
Cl
H2N NH2 90º
Co
H2N NH2 Co +3
Cl
Co-ordination number = 6

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 SHAPES OF COMPLEX IONS

5 Cl Square planar
NH3
Pt 90º
Cl NH3
Pt +2

Co-ordination number = 4
O
6 O C
Octahedral
C O 4-
3-
O O C O 90º
Cr
Fe
O O C O Fe +2
C NH2
O C Co-ordination number = 6
O
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 SHAPES OF COMPLEX IONS
Geometric Isomerism e.g. [PtCl2(NH3)2]

cis trans
Cl NH3 H3N Cl
Pt Pt
Cl NH3 Cl NH3
 SHAPES OF COMPLEX IONS
Geometric isomerism

e.g. [CoCl2(NH3)4]+
 SHAPES OF COMPLEX IONS
Optical Isomerism
e.g. [Co(en)3]3+
 SHAPES OF COMPLEX IONS
Optical Isomerism

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 PROPERTIES OF TRANSITION METALS?

4) They form coloured ions.

photo by Ian Geldard

FORMATION OF COLOURED IONS
 Complexes and Color

 Complex ions will absorb color of a certain wavelength

based on the metal, the oxidation state of the metal and
the ligand.

 The ligand will determine the ∆E which will then impact

the absorbed wavelength.

 The complement color of this absorbed wavelength is

the color that is portrayed to our eyes.

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 FORMATION OF COLOURED IONS

The colour you see is what is left after some colours are
absorbed by the metal to excite electrons.
 Complexes and Color
 A color wheel (shown) will tell us the complementary
colors (opposite the wheel)

 For example green plants (actually yellow-green) will

absorb a wavelength that is associated with a violet color.

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 Complexes and Color

The relationship between absorbed and observed colors is shown below:

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 Complexes and Color
 The complex [Ti(H2O)6]3+ is observed to be purple in color
(A).
 The absorption spectra (B) shows that the absorbed
wavelengths correspond to green and yellow light whereas
all other wavelengths are transmitted (C).

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 FORMATION OF COLOURED IONS

Once ligands bond, the five d orbitals no longer have the

same energy.

Energy = h

Energy is absorbed to excite electrons from the lower d

orbitals to the higher d orbitals.

This energy is in the uv/visible region.

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 FORMATION OF COLOURED IONS

Energy
 FORMATION OF COLOURED IONS

The size of the energy gap between the d-orbitals,

and so the colour is affected by changes in:

1) the metal

[Cu(H2O)6]2+ [Fe(H2O)6]2+
blue green

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 FORMATION OF COLOURED IONS

The size of the energy gap between the d-orbitals,

and so the colour is affected by changes in:

2) the oxidation state

[Fe(H2O)6]3+ [Fe(H2O)6]2+
pale violet green

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 FORMATION OF COLOURED IONS

The size of the energy gap between the d-orbitals,

and so the colour is affected by changes in:

3) the ligands

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

blue deep blue

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 FORMATION OF COLOURED IONS

The size of the energy gap between the d-orbitals,

and so the colour is affected by changes in:

4) the co-ordination number

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

blue yellow

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 FORMATION OF COLOURED IONS
UV/Visible spectroscopy

• Frequencies at which
complexes absorb can
be measured by
uv/visible spectroscopy.

• Light is passed through

complex and the
amount passing through
measured.
FORMATION OF COLOURED IONS
 FORMATION OF COLOURED IONS
Colorimetry

• The more concentrated the solution, the more it absorbs.

• This can be used to find the concentration of solutions –
this is done in colorimeters.
• For some ions, a ligand is added to intensify the colour.
• The strength of absorption of solutions of known
concentration is measured and a graph produced.
• The concentration of a solution of unknown concentration
can be found by measuring the absorption and using the
graph.

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 FORMATION OF COLOURED IONS

Colorimetry
69
70
 PROPERTIES OF TRANSITION METALS?

3) 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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 Catalysis
• Catalyst = substance that speeds up reaction
without being used up.
• They provide an alternative mechanism with lower
activation energy.

• For an equilibrium, they speed up both reactions

equally and so do not effect equilibrium position.

• Heterogeneous catalyst is in different phase to the

reactants.
• Homogeneous catalyst is in the same phase as the
reactants.

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 HETEROGENEOUS CATALYSTS
• Usually a solid catalyst and gaseous reactants.
• Most industrial catalysts are like this (e.g. Haber,
Contact).

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 HETEROGENEOUS CATALYSTS
1) Reactants adsorbed onto surface (onto active sites).
• weakens bonds
• brings molecules closer
• more favourable orientation
2) Reaction takes place.

3) Products are desorbed (leave the surface).

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HETEROGENEOUS CATALYSTS
 HETEROGENEOUS CATALYSTS
Strength of adsorption:

Too strong (e.g. W)

• Reactants cannot move round surface.

• Products cannot desorb.

Too weak (e.g. Ag)

• Reactants not adsorbed.

Ideal (e.g. Ni, Pt)

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 HETEROGENEOUS CATALYSTS
Specificity

Cu catalyst - dehydrogenation Al2O3 catalyst - dehydration

CH3CH2OH → CH3CHO + H2 CH3CH2OH → CH2=CH2 + H2O

Spacing of sites suitable to bond O-H Spacing of sites suitable to bond C-O
 HETEROGENEOUS CATALYSTS
Nature of catalyst

• Large surface area.

• Spread thinly over ceramic

honeycomb.
 HETEROGENEOUS CATALYSTS
Poisoning

• Some substances may block active sites (i.e. they

adsorb and will not come off). Can ruin catalyst.

e.g. S in Haber process

e.g. Pb in catalytic converters

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 HOMOGENEOUS CATALYSTS
• Most examples involve reactions in solution with
catalyst in solution.

• Some gas phase examples.

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 HOMOGENEOUS CATALYSTS
1) Catalyst reacts with a reactant to form
intermediate.

2) Intermediate reacts to form product faster than

original reactant (and regenerates catalyst).

e.g. acid catalyst

X + Y  products

1) X + H+ → HX+

2) HX+ + Y → products + H+
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 HOMOGENEOUS CATALYSTS
e.g. acid catalyst in esterification
e.g. CH3COOH(l) + CH3OH(l)  CH3COOCH3(l) + H2O(l)
O

R C OH
No H+ catalyst
SLOW step O H

+
H

O OH O
+
-H
R C OH R C OH R C O R

With H+ catalyst O H

FASTER R © www.chemsheets.co.uk A2 044 12-Jul-12

 HOMOGENEOUS CATALYSTS
e.g. transition metal catalyst

works by metal varying oxidation state

Fe2+ or Fe3+

e.g. 2 I- + S2O82- → I2 + 2 SO42-

Slow because both negative ions so repel.

1) 2 Fe2+ + S2O82- → 2 Fe3+ + 2 SO42-

2) 2 Fe3+ + 2 I- → 2 Fe2+ + I2

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 HOMOGENEOUS CATALYSTS
e.g. transition metal catalyst

works by metal varying oxidation state

Mn2+
2 MnO4- + 16 H+ + 5 C2O42- → 2 Mn2+ + 8 H2O + 10 CO2

the reaction is catalysed by one of the products

(Mn2+) – this is called autocatalysis

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 USES OF SOME COMPLEXES
V2O5 Catalyst in Contact process

Mn2+ Autocatalyst in MnO4 / C2O42- titrations

haemoglobin Contains Fe2+ – allows O2 to bond and

carried to where needed
[Pt(NH3)2Cl2] cis platin – anti-cancer drug

[Ag(NH3)2]+ Used in Tollen's reagent to distinguish

aldehydes and ketones
[Ag(CN)2] - Used in silver electroplating

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Platinum complexes as anti-cancer drugs

© Sami
Nieminen 88