8 Transition Elements Notes 1

13.
1 First-row d-block elements – the transition elements

have characteristic properties; these properties are related to their all having
8.1 d-block
incomplete elements
d sub-levels
■ The d-block metals

d-block elements are found between groups 2 (s-block) and 13 (p-
The d-block metals are a group of metals that occur in a large block between group 2 (s-block)
block) inand
the periodic
group table
13 (p-block) of the and include
periodic some
table (Figure of the
13.1). These mosthave
elements widely used
similar physical
and chemical properties.
elements in everyday life.
ure 13.1 Position Group 1 2 13 14 15 16 17 18
d-block metals s-block p-block
Period
periodic table
1 H He
2 Li Be B C N O F Ne
3 d-block
Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uno
lanthanide elements f-block
actinide elements
8.2 d-block elements
Across the d-block, electrons are being added to a d-sub-shell. They
are metals and are good conductors of heat and electricity.
They are hard, strong, and shiny, and have high melting and boiling
points.
These physical properties, together with fairly low chemical reactivity,

make these metals extremely useful.
8.3 Electronic configurations in the d-block elements
The electron arrangements for the 3d 4s
1 2
elements in the first row of the d- Sc [Ar] 3d 4s
2 2
block is shown on the right. Ti [Ar] 3d 4s
3 2
V [Ar] 3d 4s
In general there are two outer 4s 5
Cr [Ar] 3d 4s 1*
electrons and as you go across the 5

Mn [Ar] 3d 4s 2
period, electrons are added to the 6

Fe [Ar] 3d 4s 2
inner 3d sub-shell. 7
Co [Ar] 3d 4s 2
8 2
Ni [Ar] 3d 4s
This is because he 3d sub-shell is at 10 1*
Cu [Ar] 3d 4s
a higher energy level than the 4s sub- 10 2
Zn [Ar] 3d 4s
shell.
▲ Figure 2 Electronic arrangements of
8.4 4s vs 3d
As the shells of electrons get further and further from the nucleus,
successive shells become closer in energy. Thus, the difference in
energy between the second and third shells is less than that between
the first and second.
By the time the fourth shell is reached, there is an overlap between the
third and fourth shells.
From potassium onwards, the orbitals of highest energy in the third

shell (i.e. the 3d orbitals) have higher energy than that of lowest energy
in the fourth shell (the 4s orbital).
8.5 4s vs 3d
4p (max. : 6 electrons in 3 orbitals)
Orbitals in
the 4th shell 3d (max. : 10 electrons in 5 orbitals)
4s (max. : 2 electrons in 1 orbital)
3p (max. : 6 electrons in 3 orbitals)
Orbitals in
the 3rd shell
3s (max. : 2 electrons in 1 orbital)

Fig 25.1 Relative energy levels of the 3s, 3p, 3d, 4s and 4p orbitals before they contain electrons
than the 3d sub-shell.
8.6 means
This 4s that
vs 3d
potassium and calcium have the electron structure [Ar]4s1
2
and [Ar]4s respectively (Table 15.1).
The 3d sub-shell is ‘on average’ nearer the nucleus than the 4s sub-
shell, but at a higher energy level. So, once the 3s and 3p sub-shells are
Table 15.1 Electron configurations from potassium to zinc in Period 4 of the Periodic
filled at argon, further electrons go in the 4s sub-shell because it has a
Table. ([Ar] represents the electronic configuration of argon.) Note the way that the
lower energy
electron level than
configurations the 3d sub-shell.
for chromium and copper atoms do not fit the general pattern.
Element Symbol Electronic structure
Hence, potassium and calcium have, respectively, one and two
electrons in the 4s sub-shell. s,p,d,f notation Electrons-in-boxes
notation
Potassium K [Ar]4s1
[Ar] ↑
Calcium Ca [Ar]4s 2 ↑
[Ar] ↑
1 2 ↑
Scandium Sc [Ar]3d 4s [Ar] ↑ ↑
2 2 ↑
Titanium Ti [Ar]3d 4s [Ar] ↑ ↑ ↑
Table 15.1 Electron configurations from potassium to zinc in Period 4 of the Periodic
Table. ([Ar] represents the electronic configuration of argon.) Note the way that the
8. 7 Electronic configurations in the d-block elements
electron configurations for chromium and copper atoms do not fit the general pattern.
Element Symbol Electronic structure
Once the 4s sub-shell is filled at calcium, electrons enter the 3d level.
s,p,d,f notation
Electrons-in-boxes
Therefore, scandium has the electron structure [Ar]3d14s2, titanium has
notation
the electron structure
Potassium K [Ar]3d 4s
2 and
[Ar]4s
2 1
so on. [Ar] ↑
Calcium Ca [Ar]4s 2 ↑
[Ar] ↑
1 2 ↑
2 2 ↑
↑
Vanadium V 3
[Ar]3d 4s 2 [Ar] ↑ ↑ ↑ ↑
Chromium Cr 5
[Ar]3d 4s1 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
5 2 ↑
Manganese Mn [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
↑ ↑
1 2 ↑
8.8 Electronic configurations
2 2
in the d-block elements
↑
↑
Vanadium V 3
[Ar]3d 4s 2 [Ar] ↑ ↑ ↑ ↑
Chromium Cr 5
[Ar]3d 4s1 [Ar] ↑ ↑ ↑ ↑ ↑ ↑
5 2 ↑
Manganese Mn [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
6 2 ↑ ↑
Iron Fe [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
7 2
↑ ↑ ↑
Cobalt Co [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
8 2 ↑ ↑ ↑ ↑
Nickel Ni [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
10 1 ↑ ↑ ↑ ↑ ↑
Copper Cu [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
10 2 ↑ ↑ ↑ ↑ ↑ ↑
Zinc Zn [Ar]3d 4s [Ar] ↑ ↑ ↑ ↑ ↑ ↑
8.9 ions of d-block elements
When transition metals form their ions, electrons are lost from the 4s
sub-shell before those in the 3d sub-shell.
E.g. Fe2+ ions have the electron structure [Ar]3d6 rather than [Ar]3d44s2
and V3+ ions have the electron structure [Ar]3d2 not [Ar]4s2.
8.10 ions of d-block elements
When empty, the 4s level is energetically more stable than the 3d level.
However, once the 3d level is occupied by electrons, these repel the 4s

electrons even further from the nucleus.
The 4s electrons are therefore pushed to a higher energy level, higher

than the 3d level now occupied.
Hence, when transition metal atoms form ions, they lose electrons from
the 4s level before the 3d level.
8.11 ions of d-block elements 13.1 First-row d-block e
3.3 The 3d
rgy levels on
e first row of
k
pushed to a higher energy level, higher in fact than the 3d level now occupied.
Consequently, when transition metal atoms form
8.12 electronic structures of Fe, Fe and Fe ions,
2+ they lose electrons
3+ from
he 4s level before the 3d level.
Atom/ion Electron structure

3d 4s
Fe [Ar]
2+
Fe [Ar]
3+
Fe [Ar]
2+ 3+
Fig 25.5 The ‘electrons-in-boxes’ representation of the electronic structures of Fe, Fe and Fe
The relative stabilities of the +3 and +2 states in manganese and iron can be
8.13 electronic structures of Mn, Mn and Mn
nterpreted using an ‘electrons-in-boxes’ representation 2+
of their 3+
electronic
tructures (Figure 25.10).

3d 4s
Mn [Ar]
2+
Mn [Ar]
3+
Mn [Ar]
Fe [Ar]
8.14 Skill check 242
4
(a) Complete the electron conﬁgurations for Ni and Ni .2+
3d 4s
Ni [Ar]
Ni 2+
[Ar]
(b) The presence of electrons in d orbitals is responsible for the colours of transition
compounds.
(i) The d orbitals in an isolated transition metal atom or ion are all at the same ener
What term is used to describe orbitals that are at the same energy level?
8.15 Skill check 247
4
4
(a) Cobalt is a transition element and forms compounds with oxidation numbers +2 and +3.
(a) Cobalt is a transition element and forms compounds with oxidation numbers +2 and +3.
Complete the electronic structures for
Complete the electronic structures for
a cobalt atom, 1s22s22p6.................................
a cobalt atom, 1s22s22p6.................................
cobalt in the +3 oxidation state. 1s 2s 2p .................................
2 2 6
cobalt in the +3 oxidation state. 1s 2s 2p .................................
2 2 6
[2]
[2]
(b) (i) In an aqueous solution of cobalt(II) sulfate the cobalt forms complex ions.
(b) (i) In an aqueous solution of cobalt(II) sulfate the cobalt forms complex ions.
What is meant by the term complex ion?
What is meant by the term complex ion?
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [1]
8.16 Skill check 7
(a) Complete the table to show the total number of unpaired electrons in the 3d and 4s orbitals of
each isolated gaseous atom.
number of unpaired electrons

3d 4s
Cr
Mn
Fe
[2]
(b) Solid potassium manganate(VII), KMnO4, decomposes on heating to form

manganese(IV) oxide, potassium manganate(VI) and a colourless gas.
8.17 Skill check
Q. State the electronic configurations of the following atoms or ions:
i Cr3+
ii Co
iii V3+
iv Ni2+
v Cu+
8.18 What is a transition element?
While all transition elements are also 3d-block elements, not all 3d-
block elements are transition metals.
This is because even though they all share the same physical
properties, they do not share the same chemical properties.
The simple definition of transition metals as ‘d-block elements’ is

incorrect because it leads to the inclusion of scandium and zinc as
transition elements.
The problem with these two elements (Sc and Zn) is they show some
obvious differences to the other metals in the first row of d-block
elements.
• They have only one oxidation state in their compounds (scandium +3,
zinc +2), whereas the others have two or more.
• Their compounds are usually white, unlike the compounds of

transition metals which are generally coloured.
• They show little catalytic activity.

The formal definition of a transition element is that it is a d-block
element that forms at least one stable ion with a part full d-shell of
electrons.
Scandium only forms Sc3+ (3d )

in all its compounds, and zinc only
0
forms Zn (3d ) in all its compounds. They are therefore d-block

2+ 10
elements but not transition elements.
Sc 1s2 2s2 2p6 3s2 3p6 3d1 4s2 Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2
Sc3+ 1s2 2s2 2p6 3s2 3p6 Zn2+ 1s2 2s2 2p6 3s2 3p6 3d10
8.21 d-block elements
The reason why all transition elements form a coloured solution is
because their electrons transition from a lower energy state to a higher
energy state in the partially filled d-sublevel.
Therefore, electrons of an element with ions having completely empty

or completely filled d-sublevel will not transition and hence will not be
considered transition metal.
On the contrary, e.g., Fe and Cu have all or at least one ionic form that
has a partially filled d-sublevel, respectively.
3d level. However, once the 3d level is occupied by electrons, these repel the
4s electrons even further from the nucleus. The 4s electrons are therefore
8. 22 d-block elements
pushed to a higher energy level, higher in fact than the 3d level now occupied.
Consequently, when transition metal atoms form ions, they lose electrons from
Both ions of Fe have a partially filled d-orbital, therefore Fe is a
he 4s level before the 3d level.
transition element.
3d 4s
Fe [Ar]
2+
Fe [Ar]
3+
Fe [Ar]
2+ 3+
Fig 25.5 The ‘electrons-in-boxes’ representation of the electronic structures of Fe, Fe and Fe
3d level. However,distribution
once the 3dof level
4 is
charge2 occupied4
around 2 by anelectrons,
atom. these repel the
more stable morethan stable
[Ar]3dthan 4s[Ar]3d
. The extra
4s . The
stability
extra of
stability
a half-filled
3dThe 4s electrons are therefore of4s a half-f
sub-
4s electrons even further from the nucleus.
dium
nium
pushed 8. 23
from
to a d-block
the
[Ar]
[Ar]
higher from
occupation
Copper
energy elements
the occupation
atomsof
level, each
have
higher orbital
an
inof eachby
electron
fact thanorbital
one electron
by
structure
the 3d one
level which
electron
[Ar]3d
now
10produce
4s which
occupied.
1
(Figu
distribution
Consequently,+ when distribution
of
[Ar]3d charge
9 2 of
4s . In
transition around
charge
thisatoms
metal an around
case, it atom. an
appears
form atom.
that lose
ions, they [Ar]3d 10 1
4s with
electrons from a
dium While Cu does
[Ar] and not
a have a partially
half-filled 4s filled
sub-shell d orbital
is and
more does
10
stable not
1 form
than 10a
[Ar]3d 1 9
4s
he
nium 4s Copper
level before
[Ar] atoms
Copper
the have
3d atoms
an
level. electron
have an structure
electron structure
[Ar]3d 4s
[Ar]3d
(Figure 4s 25.3)
(Fig
mium coloured[Ar]solution,
9 2 Cu 2+ does, and hence Cu is a transition metal.
9 2 10 1 10 1
[Ar]3d 4sElement
[Ar]3d
. In this4scase,
. In this
it appears
case, itthatappears
[Ar]3d that 4s
[Ar]3d
with
Electron structure a
4sfilled
with 3d a
Atom/ion Electron structure 9 2 9
nium and a half-filled
[Ar] and a half-filled
4s sub-shell 4s sub-shell
is more stable
is morethan
stable
[Ar]3d
3d than 4s[Ar]3d
. 4s
mium [Ar]
[Ar] 3d 4s
Element Element Electron structure
Electron structure
mium
ed in the [Ar] 3d 3d
[Ar] Scandium [Ar]
per
lude Cu Fe [Ar]
[Ar]
elements:
ed
5.3inThe
the– ‘electrons-in-boxes’
oxides red [Ar] representation of the electronic configurations of certain transitio
per
lude Cu
Fe Scandium
2+
+ [Ar]
[Ar] [Ar]
Scandium
Titanium [Ar]
[Ar]
olet
elements:
5.3 The– ‘electrons-in-boxes’
doxides red representation of the electronic configurations of certain transitio
per
olet Cu
Fe2+
3+ [Ar]
Titanium[Ar] Titanium
[Ar]
Chromium [Ar]
[Ar]
2+ 3+
5.325.5
Fig The The
‘electrons-in-boxes’ representation
‘electrons-in-boxes’ representationofofthe
theelectronic
electronic configurations
structures of Fe,ofFecertain transitio
and Fe
8. 24 d-block elements vs transition elements
e elements from titanium to copper lie within the d-block elements
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Figure 1 The d-block elements (shaded) and the transition metals

tlined)
8.25 Characteristics of the transition elements
Transition elements as those elements that form one or more stable
ions with incompletely filled d orbitals.
They show variable oxidation numbers in their compounds.
They form coloured ions in solution.
They can act as catalysts both as the elements and as their

compounds.
They form complex ions.

8.26 Physical & Atomic Properties
s block d-block
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
Electronic configuration [Ar] 4s1 4s2 3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2
Melting point/°C 1541 1660 1887 1857 1244 1535 1495 1453 1083 420
Atomic Radius/nm 0.24 0.20 0.16 0.15 0.14 0.13 0.14 0.13 0.13 0.13 0.13 0.13
Density/g cm—3 0.86 1.5 3.0 4.5 6.1 7.2 7.4 7.9 8.9 8.9 9.0 7.1
First IE/kJ mol—1 630 660 650 650 720 760 760 740 740 910
Second IE/kJ mol—1 1240 1310 1370 1590 1510 1560 1640 1750 1960 1730
Third IE/kJ mol—1 2390 2650 2870 2990 3250 2960 3230 3390 3560 3800
8.27 Melting points
The melting and boiling points of the 3d-block metals are generally
much higher than those of the s- and p-block metals.
This is because not only the 4s electrons but also the 3d electrons are
involved in the metallic bonding.
The conductivities of the 3d-block metals are similar to those of

calcium; the conductivity of copper is particularly high.
8.28 Atomic radii of d-block elements
Across Period 3 from sodium to argon, electrons are being added to the
outer shell, while the nuclear charge is increasing by the addition of
protons. The added electrons, entering the outer shell, add not
additional shielding from the extra nuclear charge.
Hence, atomic radii decrease sharply from sodium to argon. At the

same time, electronegativities and ionisation energies steadily rise.
The increasing number of outer-shell electrons from sodium to argon

also results in major differences in structure and chemical properties
from one element to the next.
However, this is not the case with d-block elements. Electrons are
being added into the inner 3d sublevel which increases the shielding
effect towards the outer 4s sublevel.
So while the nuclear charge is increasing across the period in the d-

block, so is the shielding effect of electrons.
The two forces almost cancel each other out and the net result is
roughly equal and relatively small decrease in atomic radii.
8.31 Trends in properties
The increasing inner d electrons across the d-block increase the
shielding effect on the outer 4s electrons from the increasing nuclear
charge, keeping the effective nuclear charge almost constant across
the d-block.
This keeps the atomic radius, ionisation energy and electronegativity

almost constant across the d-block.
radius across the series of the transition elements is much smaller than
across period 3.
8.32 Ionisation energy of d-block elements
In period 3, the first ionisation energies follow a general upward trend
from sodium across to argon.
This is caused by an increase in the nuclear charge without an increase

in the number of shielding electrons in the inner orbits.
The effective nuclear charge increases considerably, and this causes a

large increase in the first ionisation energies.
The pattern is different across the d-block.

The outer electron that is removed in the reaction:
M(g) → M (g)
+ + e−
is a 4s-electron, and it is shielded by the inner 3d-electrons (as well as

by the 1s-, 2s-, 2p-, 3s- and 3p-electrons).
Although the nuclear charge increases across the block from scandium
to zinc, the number of inner shielding 3d-electrons increases as well.
This means that the first ionisation energies of the d-block elements are
fairly similar.
across the series are much less marked than the big changes across a series
of p-block elements such as aluminium to argon. This is clearly illustrated
by the variation in first ionisation energies as shown in the figure below:
2400
He
2200 Ne
2000
1st ionisation energy/kJ mol–1 1800

F
1600 Ar
N Kr
1400
H O Cl
1200 Br
P
C As
1000 Be Zn
S
800 Mg Se
B Si Ge
600
Al
400 Li Na The transition Ga
K Rb
elements
200
0
0 5 10 15 20 25 30 35 40
Atomic number
Figure 6.1 First ionisation energies.
8.36 Successive ionisation energies
There is normally a big jump between successive ionisation energies as
a lower shell loses an electron.
For example, there is a big jump between the second and third
ionisation energies of magnesium (electron structure: 1s 2s 2p 3s )
2 2 6 2
because the third electron has to come from the second shell.
This electron is subjected to a much stronger pull from the nucleus as it

is much less shielded.
The energy levels of the 3d- and the 4s-electrons are very similar in d-
block elements and so there is no big jump in successive ionisation
energies from 4s- to 3d-.
The big jump comes after all the 4s- and all the 3d-electrons have been
removed.
The numbers in bold in the next slide refer to the first 3p-electron being
removed.
−1
Table 5.3 Difference in successive ionisation energies in kJ mol
Titanium Vanadium Chromium Manganese
([Ar] 3d2 4s2) ([Ar] 3d3 4s2) ([Ar] 3d5 4s1) ([Ar] 3d5 4s2)
1st and 2nd 649 720 937* 794
2nd and 3rd 1410* 1500* 1400 1740*
3rd and 4th 1450 1730 1780 1940
4th and 5th 5450 1680 2300 2170
5th and 6th 6120 1630 2390
6th and 7th 7900 1750
7th and 8th 7300
The * refers to the first 3d-electron being removed.
8.39 Successive ionisation energies of Mn & Mg
group 13. The term ‘transition metal’ is now reserved for those metals in the d-block that show
properties characteristically different from those in the s- and p-blocks (the representative
8.40 calcium vs transition elements
elements). Table 13.4 compares the properties of a typical transition element with calcium.
Property Transition element Calcium

Melting point Very high (>1000 °C) Lower than transition elements (850 °C)
um Density Very high Lower than transition elements

Atomic radius Smaller than calcium Larger than transition elements
Ionic radius (M2+ ion) Smaller than calcium Larger than transition elements
First ionization energy Larger than calcium Smaller than transition elements
Electrical conductivity Good, but poorer than Very good – better than most transition elements
calcium
Zinc is a d-block element that is excluded from being classified as a transition element.
A transition element is defined as a d-block metal that forms at least one stable cation with an
2+
incomplete 3d sub-level. Zinc forms only the colourless Zn ion, isoelectronic with the Ga 3+
ion, with ten electrons in the 3d sub-level.

By contrast, copper, [Ar]3d104s1, forms two simple ions (cations). In the copper(i) ion (Cu+)
the electronic configuration is [Ar]3d10. However, the more common copper(ii) ion (Cu2+) has
8.41 Skill check
Describe and explain how the density and melting point of cobalt
compare to those of calcium.
8.42 Variable oxidation states
Transition metals from Ti to Cu have electrons of similar energy in both
the 3d and 4s levels.
This means that one particular element can form ions of roughly the
same stability by losing different numbers of electrons.
Thus, all the transition metals from titanium to copper exhibit two or
more oxidation states in their compounds.
The maximum stable oxidation state frequently corresponds to the

maximum number of electrons (3d and 4s) available for bonding. For
example, manganese (3d54s2) has a maximum oxidation state of +7.
The stability of the of
The stability +2the
oxidation state relative
+2 oxidation to the to
state relative +3the
and+3higher states states
and higher
increases from left
increases fromto left
right
toacross the series.
right across This reflects
the series. the increasing
This reflects the increasing
Oxidation states of transition metals

43 difficulty
Variable
8.difficulty of removing oxidation
a 3d electron
of removing states
as the as
a 3d electron nuclear chargecharge
the nuclear increases.
increases.
The table
The below showsshows
table below all oxidation states states
all oxidation of the of
first
theseries of d block
first series of d block
The positive oxidation numbers (oxidation states) exhibited by the
elements. The ones
elements. Theshown in bold
ones shown inare most
bold are common
most commonoxidation states states
oxidation of of
transition elements
the elements.
the elements. are shown below.
Element
Element Sc Ti
Sc V
Ti Cr
V Mn
Cr Fe
Mn Co
Fe Ni
Co Cu
Ni Zn
Cu Zn
Oxidation statesstates
Oxidation +7 +7
e +6 +6 +6 +6
ies of +5 +5
+5 +5 +5 +5
m and +4 +4 +4 +4 +4 +4 +4 +4
s, not +3 +3 +3 +3 +3 +3 +3 +3 +3 +3
nnsition +2 +2 +2 +2 +2 +2 +2 +2 +2 +2 +2
nne ion
+1 +1 +1 +1
.
bshell.
with
ions with
In general, the compounds
In general, of the of
the compounds higher oxidation
the higher states are
oxidation found
states in covalent
are found in covalent
lls.
ubshells.
compounds and molecular
compounds ions and
and molecular ionsthey
andcan actcan
they as oxidising agentsagents
act as oxidising as the as the
b Ni
Transition
e equation for this reaction is: elements can form ions with a variety of oxidation states (oxidation
c Cr All transition elements can form ions with an oxidation number of
numbers).
8.44 Variable oxidation states
llets rather than as a5
2, and, in addition, each element can form a number of ions with
Write the half-equation for the conversion of each of the following
oxidation numbers.
transition metalsFrom titanium
to the to manganese,
different
other
the maximum oxidation
oxidation state.
number possible
2
is
3
equal to the total number of 4s and 3d electrons. For
a
example, Fetheto Fe
maximum oxidation number possible for titanium ([Ar]3d 2
4s 2
)
Some common
ous catalyst in this reaction?
is 4band MnO
oxidation
for manganese
to Mn 2 states
([Ar]3d 5
4s2 for the transition elements and
) it is 7.
by passing the gas mixture 4
compounds c in
VOwhich
2
to V 3 these oxidation states occur:
TABLE 3.2.2 SOME COMMON OXIDATION STATES FOR THE TRANSITION
6ELEMENTS
Describe AND COMPOUNDS
the role IN WHICH THESE
of the platinum–rhodium OXIDATION
catalyst STATES OCCUR
in the catalytic
Ti converter
V of a car.Cr Mn Fe Co Ni Cu Demonstration 3.1
7 In one stage of the industrial production of sulfuric acid, sulfur dioxide+1gas Oxidation states of vanadiu
ll and highly charged. This
is oxidized to sulfur trioxide gas in the presence of a catalyst of and manganese
Cu2O
vanadium(V) oxide. The catalyst is used in pellets and the gaseous mixture
gly attract ions and small
+2 +2 +2 +2 +2 +2 +2 +2
h coordinate (dative) is passed over layers, or beds, of catalyst. The equation for this reaction is:
TiCl2 VCl2 CrCl2 MnCl2 FeSO4 CoCl2 NiSO4 CuSO4
unding molecules or ions.2SO2(g) O2(g) 2SO3(g)
+3 +3 +3 +3 +3
the transition metal cation
TiCla3 WhyVCl
is 3the vanadium(V)
CrCl3 oxide used
Mn(OH) in pellets rather than as a
3 Fe2O3
that it can donate to the single mass?
ay surround a transition+4 metal +4 +6 +4
b Is the V2O5 a homogeneous or heterogeneous catalyst in this reaction?
ding the central ion isTiO
called
2 VO2 K2Cr2O7 MnO2
at are neutral molecules c What possible advantage could be gained by passing the gas mixture
monoxide, CO. These molecules over+5
several beds of catalyst?
+7
with which they can form a V 2O 5 KMnO 4
ds include the chloride ion,

–
. 3.3 TRANSITION METAL COMPLEXES
The transition elements form ions by losing electrons from both the 4s and the
Y
the electrons in the outer shell have been removed.
45 formulae
8.The Variable oxidation states
of the common oxides of the elements from scandium to
zinc are shown in Figure 15.7 along with the stable oxidation states of each
Oxidation states and common oxides of the elements scandium to zinc
element in its compounds. The main oxidation states of the elements are
with the main oxidation states
shown in bold blue print. in bold blue.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Common Sc2O3 Ti2O3 V2O3 Cr2O3 MnO FeO CoO NiO Cu2O ZnO
oxides TiO2 V2O5 CrO3 MnO2 Fe2O3 Co2O3 CuO
Mn2O7
+7
+6 +6
+5
+4 +4 +4
+3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2
+1
Figure 15.7 Oxidation states and common oxides of the elements scandium to zinc with
8.46 Shape of d-orbitals
The d-sublevel has 5 orbitals. The shapes of the 3d atomic orbitals that
make up the 3d sub-level are shown in the next slide.
They all have the same energy (in the gas phase ions), but different
orientations in space relative to one another.
Each of them varies in their electron arrangement in space. Four of

them have shapes that look like two p orbitals configured variously
along different planes. While one looks like a p orbital surrounded by an
electron cloud doughnut.
The 3 orbital system is between the axes and 2 orbital system is along
the axes.
They are divided into two types.
The 2-orbital group where the orbitals align along the axes, eg: dx2-y2,
dz2.
And the 3-orbital group, where the orbitals align themselves between
the axes, eg: dyz, dxz, dxy.
The electron cloud of dx2-y2 is along the axes, while that of dxy is
between the axes.
Rotate
45€
→
Axe y-
'
day Axe y -
'
day
8.50 Complex ions
Metal ions exist in aqueous solution as hydrated ions.
So, Cu2+(aq), Al3+(aq) and Ag+(aq) can be represented more accurately as

[Cu(H2O)6]2+(aq), [Al(H2O)4]3+(aq) and [Ag(H2O)2]+(aq) respectively.
In these ions, the water molecules are bound to the central cation by
co-ordinate (dative covalent) bonds.
ns are 2+ 3+
can be represented more accurately as [Cu(H2O)6] (aq), [Al(H2O)4] (aq) and
+
[Ag(H2O)2] (aq) respectively. In these ions, the water molecules are bound to
mber 8.51 Complex ions
the central cation by co-ordinate (dative covalent) bonds (Figure 25.11).
H− H H− H
−
O O
H
O H H−
−
3+
H H− 2+ O− O Al H
Cu −
−
O O
−
H H
H
−
H− O
−
H
−
H −O
O
−
n which H H
H H
−
−
nions
al ion
lent)
H− H
O +
Ag O −
nion
−
−
H H
ion
inate Fig 25.11 Co-ordinate bonding in hydrated cations
8.52 Complex ions
Other polar molecules, besides water, can also co-ordinate to metal
ions.
In excess ammonia solution, Cu2+ exists as [Cu(NH3)4(H2O)2]2+(aq) and

Ag exists as [Ag(NH3)2] (aq).
+ +
In addition to polar molecules, anions can also form co-ordinate bonds

to metal ions. For example, when anhydrous copper(ii) sulfate is added
to concentrated hydrochloric acid, the solution becomes yellow-green
due to the formation of [CuCl4]2– ions.
8.53 Complex ion definition
Ions such as [Cu(H2O)6] ,
2+ [Cu(NH3)4(H2O)2] and
2+ [CuCl4] ,
2– in which a
metal ion is bonded (via dative/coordinate covalent) to a number of
molecules or anions are known as complex ions.
The molecules and anions bonded to the central metal ion are called
ligands.
Each ligand contains at least one atom with a lone pair of electrons.
These can be donated to the central metal ion forming a co-ordinate
bond.
8.54 Complex ion - coordination number
The ligands are said to be co-ordinated to the central metal ion and the
number of ligands in a complex is usually two, four or six.
The number of co-ordinate bonds from ligands to the central metal ion
is described as its co-ordination number.
Water is by far the most common ligand in complex ions.
Transition metal ions have a tendency to form complex ions because

they are small and have a high charge density.
8.55 Fe2+ complex ion
The structure of [Fe(H2O)6]2+ is shown below. H2O is the ligand in this
complex ion. The shape of this complex ion is octahedral and it is
called the hexaaquairon (II) ion.
H H
H O
H
H O
O
2+
Fe2+ H
Cu
H
O H
O
H
H
O
H H
Figure 15.13 Dative covalent bonding in an aqueous Cu2+ ion. Each water molecule uses a
lone pair of electrons to form a dative covalent bond with the central metal ion.
8.56 Cu2+ complex ion
CuSO4(anhydrous) is white, but when mixed with water, it forms a
complex ion with H2O giving the solution a blue color.
CuSO4(anhydrous) [Cu(H2O)6]2+ (copper sulfate solution)

H H
H O
H
H O
O
2+ H
Cu
H
O H
O
H
H
O
H H
Figure 15.13 Dative covalent bonding in an aqueous Cu2+ ion. Each water molecule uses a
density results in an ability to strongly attract ions and small
ules, forming a complex ion in which coordinate (dative)
8.57 Ligands
the transition metal ion to the surrounding molecules or ions.
d small polar molecules attracted to the transition metal cation
A ligand has
gands.Common ligands that are
an electron pairneutral molecules
that it can donate to include
the water, H2O;
al ion. Typically two to six ligands may surround a transition metal
ammonia, NH 3; and carbon monoxide, CO. These molecules have at
plex. The number of ligands surrounding the central ion is called
ationleast one Common
number. pair of non-bonding electrons
ligands that are with which they can form a
neutral molecules
er, H2O; ammonia, NH
coordinate 3; and carbon monoxide, CO. These molecules
bond.
t one pair of non-bonding electrons with which they can form a
ond. Negative ions that can be ligands include the chloride ion,
Negative
– ions that can be
de ion, OH ; and the cyanide ion, CN .
ligands
– include the chloride ion, Cl—;
hydroxide ion, OH ;
— and the cyanide ion, CN .
—
NAMES OF SOME LIGANDS
Formula Name O N
H H H H C O
:NH3 Ammine- H
noxide :CO Carbonyl-
n − Chloro- Cl O C N
:Cl
H
− Cyano-
:CN
– – –
Cl ; hydroxide ion, OH ; and the cyanide ion, CN .
8.58 Ligands
TABLE 3.3.1 NAMES OF SOME LIGANDS
Ligand Formula Name
H
Ammonia :NH3 Ammine-
Carbon monoxide :CO Carbonyl-
Chloride ion − Chloro-
:Cl
Cyanide ion − Cyano-
:CN
Hydroxide ion − Hydroxo-
:OH F
Water H2O: Aqua- d
CHEMISTRY: FOR USE WITH T

8.59 Ligands
Ligands are Lewis bases having lone pairs.They bond to the transition
metal ion to form a complex ion.
Six, four or two ligands combine with one metal ion, so the formation of
a complex ion may be represented as the donation of six or four or two
pairs of electrons to the metal ion.
A dative covalent bond (co-ordinate bond) is formed between each

ligand and the metal ion.
8.60 Oxidation state of complex ions
The oxidation number of a transition metal in a complex ion may be
worked out from the charges on the ligands. Ligands may be either
neutral or negatively charged.
In[Fe(H2O)6]2+ all the ligands are neutral. The overall charge on the ion is
just due to the Fe, so the oxidation number of Fe must be +2.
In [CuCl4]2— all the ligands have a 1− charge, so the total charge on all
four ligands is 4−. The overall charge on the ion is 2−; therefore, the
oxidation state of Cu must be +2.
8.61 Shapes of complex ions
The type and number of ligands surrounding the central metal ion is
indicated in the name of the complex.
The shape of the complex ion depends on the number of ligands

surrounding the cation.
These geometrical shapes are the same as those assumed by

molecules with 2 to 6 atoms (and no non-bonding electrons)
surrounding them.
The most common coordination numbers are four and six, although
some complexes have only two ligands.
According to VSEPR theory, the coordinate bonds take on the

geometric arrangement that gives the complex the lowest energy.
The shape of a complex with two ligands is linear, with four ligands it
may be tetrahedral or square planar, and with six ligands the complex is
octahedral.
These complexes do not always obey VSEPR theory rules, so although
six coordinate complexes are virtually always octahedral, four
coordinate complexes may be tetrahedral or square planar.
Silver ions often only form complexes with two ligands. This can be
explained by the larger size and single positive charge of the Ag .
+
tiful oxygen.
ketones. Repr
8.64 ShapesSynoptic
of complexlink
ions A sol
Repr
emia is a condition which may be caused by a is use
diagr
You will learn more
rtage of haemoglobin.MThe body suffers fromabout a Alde
M visua
using Tollens’ reagent
of oxygen and the symptoms include fatigue, to test keton
shap
for aldehydes and ketones
athlessness, and a pale skin colour. The causes may in tube
of th
octahedral tetrahedral
Topic 26.2, Reactions of the
oss of blood or deficiency of iron in the diet. The latter Com
carbonyl
y be treated by taking group in
‘iron’ tablets aldehydes
which containand Isom
(II) sulfate. ketones.
M M
Repr
You
with
Repr
square-planar linear of th
diagr
geom
2 2
plex ions
2
ions with a co-ordination number of 4 thatNH 3
Most complexes Pt
are
2+ formed by ions. However, it is also possible to fo
gle 90°
8. .
65 – Linear
a complex using the uncharged metal atom. For example, nickel, iron
– Cl
sobond
form co-ordinate
chromium
angle 180°.
bonds
all –
form toa metal
complex with carbon monoxide. The three comp
I) sulfate
If is added to Cl
concentrated NH
–the complex
are
A contains
illustrated
few complexes two
in ligands
Figure
with (co-ordination
6.8. 3 number 2), it is
Cl
n Figure
linear;6.7.examples
ow-green due to the formation
a are the
co-ordination CuCl
number and
2 of
− [Ag(NH
Cl 3 2 ions.
– ) ]+
of 4 are planar Pt2+
2+ –
Cl
2+ 2–
] and [CuCl4] , in which a
– –
Cl
ecules or anions are known as Cl
–
of Cl
– + – H N Ag + NH
nded to Cl
the Cu
central metalCl ion 3 3
dral
ast one atom with
Complexes with aa lone pair of
l metal ion forming
co-ordination a co-ordinate
number
A few complexes with a Complexes with a
of 2 are usually linear
a to the central metal
co-ordination ion and number
co-ordination co-ordination number
sually
yex two, have
four or six. The of 4
number have a
is said to show six-fold co-ordination; square planar of 2 have a
rrangement
lexes show four-fold square-planar
co-ordination. linear arrangement
ral
nds. metal ion is described as its
arrangement of ligands. of ligands.
by
central metal ion by a dative O Hor
H central
H atom are repelled as far as possible.
H O
● in
O complexes with a co-ordination number of four, the ligan
co-ordinate bond. H H H
8.66 Octahedral complex - [Cr(NH ) ]

H occupy tetrahedral positions, although there are a few comp
A co-ordinate bond is a O
dative 3 6 3+
Figure 6.4 The [Cu(H2O)6] ion. 2+
H O
fourfold co-ordination, such as [Pt(NH3)2Cl2], with a square
H H H
covalent bond formed between the structure.
Figure 6.4 The [Cu(H O)
A range of complex ions can ion.
ligand and the central ]2+
ion.
metal be formed with a variety of central in complexesOwith a co-ordination number of two, the ligan
● cations
Complexes with a co-ordination number of 6
2+ have an octahedral
2 6
a
Cu linear structure with the central metal ion.
2. 36 Shapes of Complex Ion
A complex
and a range ion is an ion in which
of surrounding ligands. Ammonia H is an effective ligand and, for H
A range offorms
complex ions or can be formed 3+with a variety of central cations
arrangement
and
a number
example,
area bound
range to
the of
of moleculescomplex
of asurrounding ligands.
central cation
anions
[Cr(NH
ligands.
3
) 6
] (Figure
O 6.5). These structuresHare all illustrated in Figure 16.17.
by Ammonia is an effective ligand and, for O
example, forms
co-ordinate bonds.the complex [Cr(NHNH
3
)
3 6
]3+
H (Figure 6.5). NH3
H
O
NH3
H H
H3N Figure 6.4 The [Cu(H2O)6]2+ ion.
H3N
H3N
A range NH
of 3complex ions can be formed with a variety of central cations NH3
Cr3+ and a range of surrounding ligands. Ammonia is Cr an3+effective ligand and, for
example,NH
forms
3 the complex [Cr(NH )
3 6
]3+
(Figure 6.5).
H3N Cr3+ H3N
NH3 –
NH3 NH3 Cl
H3N
NH3
Complexes with a
H3N
co-ordination number of
NH3 6 are usually octahedral NH3
Cr3+
Figure 6.5 The [Cr(NH3)6]3+ ion. NH3 NH3
– 3+
Figure 25.7N coordinate bonds with
Figure the
25.7three
C C N Figure 25.14
central metal ion. This makes
shows N Cexamples
C N
Even 8. 67
The
Multidentate
−
OOC–H
ion
ifligand.
the Octahedral
making
2C coordination
H
the
ligands
The resulting
attachment
Hion is
complex
number
called
via
CHa
a lone
–COO
complex
2 of
pair
−
a
ion.
-
of
EDTA [Cu(H
electrons
complex
is
2 O)
called
multidentateisEven
−
46]a 2+
and
Multidentate
or
OOC–H if
2,
3+the
2 C coordination
water ligands
can
H only
H n
n The ion making the attachment via a lone pair hexadentate
of electrons H 2 O
is called a NH 3
ever
Ligands
r
actAn as a
example
Complexes
ligand. monodentate
thatTheform
of a
with many
complex
resulting a ion withligand
coordinate
co-ordination
ion is called water as
a complex due
a ligand
number
to
ion.bonds
is the
[Cu(H position
2 to
O)
Hof2O6 have 6 a
]2+ever act
Ligands
metal
(Figure
an OH of
6.4).
octahedral
the
as
atomalone pairs
monodentate
that form 3Nmany
or Hion of
are
Figure 25.9 Figure
2+electrons.
2
25.9
electrons.
n
called
alled multidentate
arrangement
An example of of
a ligands.
complex Hligands.
ion with
H
water Anas a example
ligand is [Cu(H of
O) Fe] a multidentate
called
(Figure multidentate
6.4). ligand Co
is
liga
ror 2 6
TIP
Figure
EDTA . 4− 25.14 shows three
H H O H
examples of octahedral
H 2O TIP
Figure
EDTA
4−
OHions.
2 4− 25.14
. shows
H 3 N three
Six lone pairs
Remember thatHligands
Multidentate
or the are
ligands shown on the diagram. EDTA
H 2 O Six canlone form
Remember thatligands
Multidentate the pairs
ligand sixare shown
coordinat NH 3
3+ H O 2+ 3+
2+
bonds
EDTA
attached
n the is with
an O
the central
abbreviation
H2Oto a wedge-shaped bondNH3 metal
for ion and so as
ethylenediaminetetraacetic
H well as
bonds
EDTA
attachedbeingis with
andescribed
acid. the
abbreviation
The
H2Oto a wedge-shap as
central
structur m f
Ligands that form many coordinate bonds to
[Fe(H Ligands
a
O) metal
] 2+ that
atom form
or ion many
are
[Co(NH
multidentate,
on. H O
of
are
en EDTA
the2comingKeyis given
out
OH
terms it H
isinalso
OFigure
2of the screen described
H25.8.
3 N OTheas
Hionhexadentate.
NH
making
3 the ofmultidentate,
are
attachment
2 6 EDTA
H 2
3coming
N
Ovia a is
lone given
out
NH
OH
pair it
of
2
3 is
of in also
Figur
the
electrons isde
screca3
called
ch Hmultidentate ligands.
Cu 2+
An example of called
a multidentate
multidentate ligand liga
is
TALS METALS
Fe ligand.
Co H The resulting ion is called a complex
Fe
Cu ion.
or
ons paper
on.
4− A towards
ligand is a you.
molecule Those
or anion O Figure 25.14 or paper 4− towards you. Tho
EDTA
ch H O .
H thatTIP
O
OH Cu2+
H N HAn example
NH of a complex EDTA
ion Hwith
O
N water. as a ligand
OH
NH is [Cu(H O) ]2+
attached
by
ons
2
HH O
to a
has dashed
at
H H bond
2least one lone pair 3O
are NH
H
The
3
attached
6-coordinated
2
3
H O
to a dashed
copper(II)
2
3
H
2
H bond
6
comp
HOOC–H22C O
Remember
of electrons and bonds that
to a CH
the2 –COOH
ligands
H 3 HOOC–H 22C
behind
by the
EDTA isH central plane
an abbreviation of the
metal ion by a dative screen
for
O or
or
O H
complexes
H behind
EDTAas
H
the isthean
acid.
top plane
abbreviation
and The of the
structu
bottom sc f
li
paper. The attached
two ligands to a wedge-shaped
attached bond paper. The two ligands att
NSITION
O
of EDTA N C C N of EDTA is Ngiven C C
2+ ] 2+ in Figur N
[Fe(H2isO)given in Figure 25.8.
co-ordinate bond. H H H
are
6] 2+
A co-ordinate coming
bond out
is] a ion.O
dative of the
H
[Co(NH
screen
3) 6] These
2+
ligands are
[Fe(H
[Cu(NH often
3 )24O)
(H 2
6 ]
O) not
2 replaced
o the solid
Figure bonds
6.4 The [Cu(H are
O) above
2+
and H O to the solid bonds are abo
HOOC–H 2C
469839_25_AQA_Chem_510-535.indd
Figure 25.14 covalent bondH
2
formed
H
6
Hbetween
or paper towards you. Those CH
H
514the
2 –COOH ligand replacements
HOOC–H
Figure 25.14 H
2 C reactions.
H
H
below Athe
Figure plane
6.4
ligand The
and the of
[Cu(H the
O) ]
central rest.
ion.
metal ion.2+ below
range of complex ions can be formed with a variety of central cations the
O
plane of the res
H H
2 6
H H 2+
ligands
b Deducein cisEand trans of
values M (aq) → M 4(aq) + e for the systems in
isomers
exist
Figuremolecules,
25.9. Then decide which • complexes
ofalso
these with a
systems couldco-ordination
be oxidisednumber
by: of two usua
Other polar besides water, can co-ordinate to metal ions. In excess
8.68Cr2O
ammonia Octahedral
7
2–
solution,
(aq) Cu
+
2+
14H + complex
exists
(aq) as
+ 6e–
[Cu(NH
→ 3) -
(H
2Cr
4
[Fe(CN)
arrangement
2
3+
O) ]
(aq)
2
2+ of
(aq)
+ 7H 6 ]3—
ligands
and
2
Ag
O(l)
(Figure
+
for
25.12).
exists
which as
+
[Ag(NHE3)2=] +1.33
(aq). V.
–
CN
■ C
–
Cl form co-ordinate bonds to metal
In addition to polar molecules, anions can also 3–
CN Cl –
ions. For example,
NC–
CN
hydrochloric acid, the solution becomes yellow-green due to Cl
the ■ Complex ions
when anhydrous copper(II) sulfate is added to concentrated
3–
formation
2–
of
A d-b
– –
CN Cl
2–
[CuCl4] ions. Fe NC CNPt 2+ C
3+
Fe2+
A d-block –
metal complex ofion
lig
C
NC – NC CN Co
2+ NC
Cl
CN
2+
Ions such as [Cu(H2O)6] – , [Cu(NH Fe ) (H O) ] and [CuCl ] Co
2–
, in which a
CN Cl– 3 4 2 2
of ligands.
Cl 4
These are Cl–molecul
ligan
metal ion is associated NC with a number CN
of molecules or anions
Cl CN
– are known Cl as
complex ions. The molecules and anions bondedligands to theCl are water
central metal ion molecules, OHCHH −
3N
,
are called ligands.– Each ligand CNcontains at least one atom − with a lone pair of −
CN
electrons. These can be donated to the central Cl– OH , and
metal ionoctahedral
forming
cyanide
a
ions,
co-ordinate
CN T .
A few complexes with a
bond.Complexes
The ligands are saidoctahedral
to
with a co-ordination be co-ordinated to the The
Complexes with a co-ordination tetrahedral
central ligands
metal ion share
and
co-ordination number their
bond lo
sq
the number number of 6 have in
of ligands an a complex
octahedral arrangement ofCN
number of 4 usually
3–
is usually bonds
two,have
a tetrahedral arrangement
four or formed
six.
Cl
The between
of 42–
numberhave a
square-planar
the d-b
They
of co-ordinate bonds
3– ligands.
CN co-ordination number. Cl
from ligands to the central metal ion is
of ligands. They are sometimes
2– described –
arrangement as its
called Cl
paircod
of ligands.
NC CN Cl
pair donors) Cl
Co (Chapter 18). T
Fig 25.12 The structure of complex ions
Fe
EDTA ever
Ligands
Co .act as
thata monodentate
form many Co ligand
coordinate due to
bondsH the
O position
to a metal
OH of the
atom lone or pairs
HionN areof
EvenFigure if the 25.9coordination number of a complex is 4 or 2, water can only 2 2 3
electrons.
called multidentate ligands. An example ofFe a multidentate ligand Co
is
− 8.
ever act69 as a Octahedral
monodentate
H H complexes
ligand due
−
The
to six
theexamples
lone pairs
position are shown
of the lone pairs of
TIP
OOC–H Figure
EDTA 2 C 4− 25.14
. shows CH
three 2–COO
examples on the of octahedral
H2O These OH
diagram. ions.
form 2 H3N
electrons.
Six lone pairs are shown on the diagram.
coordinate EDTA
bondsH O 4−
with can
the form six coordinat NH
FigureRemember
25.7N
Multidentate Cthatligands
Cthe
3+
ligands
N Figure 25.14
2+
2
shows three examples 2+ of
bonds
EDTA iswithan the central
abbreviation metal
for ion central
and metal
so
ethylenediaminetetraacetic as ion.
well Thisas makes
being described
acid. The as
structu
attached
Ligands H 2 O to
that a wedge-shaped
form many bond
coordinate NH 3 bonds
− EDTA multidentate to a
and metal H 2 O
atom or ion are
Even
−
OOC–H
of
are if
Multidentate the
EDTA
H 2
2
C
multidentate,
coming
O coordination
is ligands
given
Hout
OH it
2of
Hisin
the number
also
FigureCH
screen 2–COO
described
25.8.
H 3 Nof a complex
as hexadentate.
NH 3
is
[Fe(H4 2or
O) 6 2,
]H
3+
2+
3Nwater can NH only
3
[Co(NH
called multidentate ligands. An hexadentate
example H 2 O of a multidentate ligandNH 3 is
ever
Ligandsoract as
that
paper a Femonodentate
form
towards many you. ligand
coordinate
Those due Co to
bondsH the
O position
Figureto a metal
25.14
OH of the
atom lone
Cu or Hpairs
ionN of
are NH
Figure
EDTA 25.9 4− . 2 2 3
electrons. H O OH H N NH H N NH
called attached
2
multidentate
H O
to a dashed
2
H bond
ligands.
H are
An3
example
NH The
3
of Fe a multidentate
6-coordinated
3
H O
ligand
copper(II)
3 Co
is com
TIPEDTA
Figure
EDTA
HOOC–H
behind
4− 25.14
. isthe
22C
an shows
plane three
of the screen
abbreviation for
CH
examples 2 –COOH
or of octahedral
3H O
2
complexes 4−
OHions.
2
as the
2
acid.
top
H
and
N
The
3
structu
bottom
NH
l
Six lone
dMultidentate
Remember
paper.
pairs
Thethat N
are
twothe shown
ligands ligands
ligands
C C
on the
attached
N
diagram. EDTA
H2O can form six coordinate NH3
bondsof EDTA
with[Fe(H2isO)given
the ] 3+
2+
central in Figure
metal 25.8.
ion [Co(NH
and so ) ]
as These
2+
2+
well ligands
as being are
[Cu(NH often
) (H
described O) not
2+ ] 2+
as replace
EDTA
attached
to is
HtheOanto abbreviation
a
solid
6
wedge-shaped
bonds are for ethylenediaminetetraacetic
above bond and
NH
3 6
H acid.
O
3 4
The 2
structure
2
LigandsHOOC–H
2 that C form many coordinate
CH
3
–COOH bonds ligand
[Fe(Hto a
O) metal
replacements
] 2+
2 atom or ion
reactions. are
[Co(NH ) ] 2+
of
areEDTA
H OFigure
multidentate,
2coming
below is 25.14
given
2
theout
OH it
plane is
in
2of the also
H Figure
of described
H
screen
the 25.8.
H
rest.
3 N 2
as hexadentate.
NH 3 2 6 H 3N NH 3 3 6
calledFiguremultidentate
Fe 25.8 H ligands.
H AnCo example of a multidentate Cu ligand is
or paper
HOOC–H
The towards
C
6-coordinated you. Those
copper(II) CH –COOH Figure
complexes 25.14
are actually distorted octahedra
EDTA
H O
r attached
2
4− .
to
2
a
OH
dashed
2
bond
H
are
3 N
2
NH 3 4-Coordinated H 3N NH 3complex i
complexes
HOOC–H22C H O N H as the
CH top
C and
N bottom
CH2–COOH 3 NH ligands
The are
6-coordinated further H 2 O away
copper(II) than the
complexothe
behind
EDTA EDTA the
is anis
These plane
Cl abbreviation
ligands
usually of2−the screen or
areused for
oftenin not
Cl replaced
alkaline
−
buffered These
whensolution
complexes are
copper
as less
the common,
acid.
complexes
totop ensure
andThebottom
it and
structure
undergo
is the they
anio
ligan c
paper. HOOC–H
The N C
two ligands
C HC attached
N
H CH –COOH
of EDTA ligand
[Fe(H isO)given
2
replacements
] 2+ in
form.2All6 the acid COOH groups Figure 25.8.
reactions.
[Co(NH
2
3 6 lose
) ] These
2+ their hydrogen
ligands are 3often
[Cu(NH )4ions
(H2 not
O) to
2 form
] 2+
replaced the an w
8.70 Shapes of complexes with coordination no. 4
With four ligands, VSEPR arguments predict that the complex is
tetrahedral and this is usually the case; examples are the CoCl4 and
[Zn(NH3)4]2+ ions.
However, there are complexes with four ligands that are square planar,
which shows that factors other than electron repulsion must be taken
into account.
H2O(l) called ethane-1,2-diamine and co-ordination number
an
construction lines to show the square-
analysi
and qualitative
8.71 Tetrahedral
1,2-diaminoethane. complexes Its formula NH3
planar arrangement of the NH3 ligands FigureWhen aqueous copper ions
6.5 The [Cr(NH ) ] ion. 3+
.organic
The compounds in is H NCH
2 aqueous CH NH
2 2 solutions . Each nitrogen
24
and qualitative
NH3
2 Cu 2+
Cl – acid there is a change 3 6
in bo
Complexes
that there with a co-ordination
atom has a lone pair which number makes of 4 generally
Figure
The word6.5 The form
used
Concentrated [Cr(NH
for a
the) ] ion.
ammonia
hydrochloric ligands
3 6
3+
is ‘a
t to right. Synoptic
tetrahedral complex
it a bidentate
Cl– link
ion. ligand.
Cu2+ Cl –
the
Thenot
Do
name.
Cl
word− The
ligands:
used for
confuse
[Cr(NH
thisthe with
)
3 6
]3+
ammonia
ion
amine,
is called a
ligandsindic
which
he
is ‘a
H
elements
–
the name. The [Cr(NH3)6] ion is called a he
Cl 3+
mplexes
dinate There are some
Cl –
– further examples 2– Anions such as chloride ions, Cl , which
can also be
nsition elements and qualitative analysis

−
Do not confuse this with [Cu(H
amine, O) ]
indic2
Cl elements
es ligands.
can of ligand substitution reactions – complex ions such as [CuCl4] . 2− 2 6
Anions such as chloride ions, Cl−, can also b
6 Transition
Cl
ofSynoptic
otherFigure
metal 6.6link
ions,
The [CuCl both] ion.M and2+ The The
overall
complex
2−
pale
ionscharge
such blue
of
charges of the ions and molecules
4
as a[CuCl colour
complex
4
]2−
. ionof the
is alway
from whic
–
yellow [CuCl ] 2− ion. (Alth
6 Transition
3+ Cl
M Cl– , summarised Cu 2+
in Topic 24.3, The
in overall
this case, charge
the net of a
charge complex
4 is 2- ion
because is alway
Figur
the
EntropyKey is aterm
Figure measure
6.6 The [CuCl
Cl
] of
– the
ion. degree 2−
charges
central
4
[Cu(H of
anion the ions
O)
and Cu
fourand
]
2+
2+ molecules
will
surrounding from
remain.)
Cl
Cl – − whi
catio
A summary of acid–base and in this case, the 2 net 6 charge is 2- because The thew
ligands. of disorder (Topic 17.4, Why do in steps. The co-ordination
Chapter
The
Key co-ordination
term number of a The Cl −
ion has, in fact, four separate −lone p
f substitution reactions of some central

Cl –
anion and four surrounding Cl catio
the n
n form chemical – reactions
metal
Cl ion is take
the number place?)
of co- those is used
tetrahedral. to form the co-ordinate bond.
Do n
Chapter
metal ions. The Cl ion has, in fact, four separate lone p

−
The co-ordination number of a sharing of a lone pair of electrons.
that it
ne diamine, so the more ordinate
metal ion
bonds
molecules
is the
to the
numberthatmetal
of
ion
are
co- those is used to form the co-ordinate bond. Anio
▲ Figure 3
from The
the shape
surrounding of the [CuCl
ligands. ] 2− ion
Of the three complex ions shown above, the
y more sharing of a lone pair of electrons. comp
[CuCl
released and are
ordinate 4 ]2— free to move
bonds to the metal ion 4
number of 6 and the last one a– co-ordinatio
from the surrounding ligands. Of the three complex ions shownCl above, The theo
df stability is 122
around, the greater the entropy. Figure 6.6 The [CuCl ] ion. 2−
number of 6 and the last one a co-ordinatio 4 charg
wo 2− outer 4s electronsFe and as you go across Co
the period, Au Cl H3N
Cl ] . configuration of
is: ligands.
Cl These are molecules
ligands Cl or
are negative
water ions tha
molecules,
o the
4 innerNC CNexplains the overall
3d sub-shell. This CN Cl
h
angements
ments. 8. 72
co-ordination
The of Tetrahedral
number
arrangements four
of are ligands
complexes
square
chromium, Cr, 1s
Cl are
planar,
and water
for molecules,
22s22p63s23p63d34s2
examples OH −
ClH
, 2O,
and ammonia
Cl
cyanide molecu
ions, CN
CN − −
N ]2−
-series. . OH(3d
[Ar]pattern. The d-sub-shell is full
ite4 fit the The vanadium ion V 2+
,octahedral
and
has
10 ) in cyanide
lost
Cu the two ions, CNThe
4s2 electrons
. tetrahedral
andligands
has theshare their l
rangement
Cr and there of is only one
electron configuration:
electron in the 4sTheouterligands
shell. share their lone pair
CO with empty orb
6 3+ octahedral Cl 2 – 2– tetrahedral
2 2 6 2 2–
6 3
bonds formed
square planarbetween the d-
lf-full d-shell Cl
makes the atoms more stable in1sthe2s 2p 3s 3p 3d
ate CN 3– bonds
NC formed
Cl between
CN
2– the d-block
They are metal ion
sometimes
– and the
called c
ter main shell makes the noble gas atoms stable. Cl Cl
–
Cl
2–They are sometimes called paircoordinate
– bonds. The
donors) (Chapter 18).OCli
NC
figurations CN Cl Cl
Fe theClions of
of d-block
pair donors) (Chapter 18).
H3 Cl Cl
Co Co
Cl Cl
Ni
Co OC
The
Au number
Ni of dative
+
H 3N bo
NC Co CN TheAu numberCl of dative
H 3N
as bonds
the Agformed
H Nby
coordination
3 the ligan
numbe
CO
Cl NC
Cl
CN Cl Cl
figuration of CN Cl
the ionClof an element,asfirst
the coordination
write number. Common
Complexes with coordinatio
a coordinat
ion of the Cl
Cl Cl
element using the Periodic Table, from
Cl
– 2 –
Complexes 2–
with a coordination
CO
(occasionally number of
square 2 will
planar) be
octahedral 2
[CoCl4] [CoCl4] [Ni (CN)4]
tetrahedral square planar
[CoCl4]2— (occasionally square planar) and
complexes Tetrahedral4 with
those
[Ni(CO) may ]2+have6distort
are oc
2-diol tetrahedral square planar (a)linear
complexes
2+ may have distorted The shapes.)
Nickel tetracarbonyl
net charge on a com
le: Electron configuration
3–
Cl
2– of V – Figure 6.8 Complexes of transition metals and ca
–salt of a transition metal in water,
– ClThe copper
for example, net Clcharge on a charges
complexon ionthe is ligands
the sum(ifofth th
an atomic number of 23. Its electron
ly charged
H Clmetal
O Co Cl charges
– ion becomes surrounded by water
on
Au
the ligands (if
H
they
H NH
Ions are of
Ag
ions).
d-block H
The
N
net
metals
+ chh
O O
Mono
—
CO
ligands (Figure
Cl 1). Normally there are six water 3 3
—
2
Ions of d-block metals have a strong tendency to
2
H
1s2 C —2p
2s 2 C 3s 3p 3d 4s
6
tahedral arrangement.
2 6
Au Such 3 2
Cl species are
H called
N Ag ions.
aqua HN
+ relatively
C C
small C C
and highly
Most c
lig
3 3 –
O –
O
—
H2N
=
NH2
—
H O with the
screen to the solid bonds are above and
Those HOOC–H2C
Figure 25.14 H H CH 2 –COOH ligand replacem
8. 73 below
Tetrahedral the plane
complexesof the rest.
examples
bond are Figure
HOOC–H 25.8
C H H CH –COOH
The 6-coordinated copper(II) complexes are actuall
e screen or
2 2
4-Coordin
complexesN as the C top C and N bottom ligands are furthe
s attached Theseis ligands 2−
are often not − These are less
EDTA Cl usually used in Cl replaced
alkaline whensolution
buffered coppertoc
above and HOOC–H2C H H CH 2–COOH
ligandAllreplacements
form. the acid COOH reactions.
groups lose their hydrogen
e rest. Figure4−25.8
Cu Fe Tetrahedral
EDTA .
4-Coordinated complex ions
Cl
Cl
Cl Cl
Cl
Cl The [CuCl 4 ]2−
The six lone pairs are
−
−
EDTA
OOC–H is
2C usually H H
used in alkaline
These are less common, and they canCH 2–COO −
bufferedThe
on thetake bond
solution
up one
diagram. angl to
Theseo
Cl
form.[CuCl
All 4the
]N
2− acid
C COOH
C groups
[FeCl4]
N − lose their
coordinate
The hydrogen
bonds
above
with
com
4− central metal ion. This
Fe Tetrahedral
EDTA .
−Figure 25.15
complex − EDTA acid to [Cu(H
multidentate an
OOC–H2C H H CH 2–COO 2
Cl Cl The [CuCl ]2−, [CoCl ]2− and [FeCl ]− complexes
hexadentate ar
Cl −
OOC–H2C
The bond
Figure
4 H H 4
Stereoiso
The
4
CH2–COO on [CuCl
−
25.9 angle at the central metal atom or ion in 1
six lone
the diagram.
4
pairs
]2− is
are
Thesye
Cl NH
Cl Cl– Cu Cl Cl Cu Cl and tetra
ructure with the central metal ion (Figure 15.15).Most ligands use only one lone pair of electrons
A complex to form
ion is ana co-or
ion in w
emistry of complex ions

and ‘co-ordination number’. A co-ordination compound is one that contains
a complex ion, and the co-ordination with the
number central
Complexes
of a metal
with
complex a ion.
ion
Complexes These
is the
with ligands
a number are of described
moleculesMost oras
anio
com m
Square
8.74 Shapes ofplanar complexes
–
ClKey terms
trahedral complexes are [CuCl ]2− and [CoCl ]2− . The
H3N
–
number complex
of ions
co-ordinate
e of the chloride ions, compared to oxygen atoms
4
bonds from the because
4
ligands
in to
water
co-ordination
theythe
of 2
have
Complexes
central
are
number
only
usually
‘one
co-ordination
metal
co-ordination
linear
with
tooth’
ion.
a
to hold
number
number of
bound Cl
onto
to a the
centralcentral
metal
a comple ca
ca
Complexes
The shape with a
of a complex Cl – ion Latin
depends for ontooth).
the Examples
number
4 areof 2of of
are
usually
monodentate
usually
ligands ordinate
linear
around
tetrahedral
ligands
the bonds. include
chromiu
Monodentate
that it is Co-ordination
not possible
co-ordinationligands
for more
compounds than
form onefour ligands
dative
number of contain complexes to fit
− round
which
− may be
− cations, anions
NH Cl , OH and CN .
on. Some complexes
central metal with
ion a
(the co-ordination
co-ordination numbernumber of the of 4 a
central form
metal a square
ion).
3
covalent
orCr 3+ 4 (co-ordinate)
are usually
neutral moleculesFigure 6.7 bond
tetrahedral
(Figure with
The shapesa
15.14).of Examples
complex ions. of co-ordination compounds A ligand is a molecule are illust
or an
Some ligands have more than one lone to
pairtheofcentral metal ion
electrons thatin ca
ns. planar include:complex
In complex ion.
central metal ion in a complex.
ions with co-ordination number:
ordinate bonds with the same metal ion.ion by co-ordinate
Bidentate bonding.
(‘two-tooth
Bidentate
● K 3[Fe(CN)
ligands ] form
containing two dative
the negatively charged complex ion [Fe(CN) ]3−
● 6 NH –6
3Clthe
– shape is octahedral
Cl – for example,
and the bondform An two
angles dative
are
octahedral covalent
all
– 90°
6
complex bonds
Theis with
said tometal
co-ordination show ions in
six-f
number
covalent (co-ordinate) bonds
● Fe(NO3)3.6H 2O containing the Bidentate
with a positively charged Cl
complex1,2-diaminoethane,
ion
ligands include H NCH CH
Types of ligand
central metal ion in a complex.
[Fe(H2O)46]– the shape is sometimes
● 3+ NH
tetrahedral,ion,
ethanedioate 3
and
bond tetrahedral
C2Oangle4
2− , 109°
and
complexes
5’ but
amino
ion in
there
acids
a complex
show
are 15.16).
(Figure
ordinateNH bonds
is the
four-fold
2 num
2
to the meta
c
Most ligands4also
● Ni(CO) use onlya number
containing Pta neutral
one 2+ of pair
lone complex
complex ions
of electrons with
between to form anickel
co-ordination
atoms
aMost and number
complexes
co-ordinate carbon
bondPt 2+of
are 4 thatby ions. Howev
formed 3
the surrounding ligands.
with – monoxide
the are
central molecules.
square
metal planar,
ion. bond
These angle
ligands 90°
are .
described a as monodentate
complex using the uncharged metal atom
ber of Cl Cl –
hedral becauseNH they have only
3 ● 2 – the shape is linear
‘one tooth’ to hold onto the central cation
chromium (dens
all formis a complex with carbon m
A few complexes with NH3 with 2+
bond angle 180°.
Latin for a
tooth).
co-ordination
Examples
number
of monodentate
Co ligands
– include
are
A few H O,
illustrated
complexes
2 NH in ,Figure
with
3 15.6
NH
6.8. 3
Formation of complex
e − − − Cl
–Cl 432, OH of The
4 and
are CN
structures
planar . are illustrated in Figure 6.7. a co-ordination number
Cl 15 Transition metals
PtCl
Some ligands have more than one lone pair of electrons that can form co-
2(NH3)2 of 4 are planar
ordinate bondsClwith – the same metal ion. Bidentate (‘two-toothed’) ligands,
NH3 for example, form429two dative covalent bonds with metal ions in complexes.
69983_15_Chem_Y1-2_418-449.indd
–
Bidentate ligands
469983_15_Chem_Y1-2_418-449.indd
Complexes with a
432 include 1,2-diaminoethane, Cl H 2NCH2CH2NH2 , the
3+ethanedioate ion, C co-ordination
O 2−, and number
amino of
acids (Figure –
15.16).
Cl Cu +
Cl –
Cr 2 4
–
d as you go across the period, they can act asNi bridges
2+ between aroun
metal
figuration is: CH3 and so has an extra shell
This explains the overall two Figureions.
▲ metal 6 Haemoglobin A few
compared with the nitrogen atom the co
8.75 Square
Cr, and planar complexes
1s 22s 2 2p 63s2 3p 6 3d 3 4s 2
ers of
four
2+ are
Fe chromium,
N square planar, for geom
2+ 2Below thein Period
C
plane of 2.
this ring is a fifth C
nitrogen atom acting
The [C a
vanadiumision
-sub-shell fullV(3dhas10
CH) lost
in Cu
CH2
the two 4s electrons
– and has the N – 2+
a ligand. NThis atom is part of a complex protein calledCoglobin
,
tronN configuration:
electron in the 4s outer shell. Some
Clatoms2– more 2 –
CHstable in1s
2–
22s22p63s23p63d3
the
The sixth
▲
2+
Synoptic
site
– can
Figure
N 7 accept
A link
squarean oxygen
planar molecule
complex as
N a
– ligand.
of −1,
NC CN The Fe to O2 bond C is weak, as :O2 is not C a very goodThe
ligand
re
e noble gas atoms stable. Look back at Topic 17.4, Why do
allowing the oxygen molecule to be easily given up tolarger cells.
Synoptic link take place?, to A solu
chemical reactions
H2
Co
Cl
ions of
CH3
Cl
d-block Ni Better ligandsrevise than oxygen
entropy. Ni
You will learn more about
can
2+
bond irreversibly is
to use
aroun
the
H2COOH iron and so destroy haemoglobin’s oxygen-carrying Aldeh
A few
NC CN using Tollens’ reagent to test keton
capacity. ThisC explains the poisonous C effect of carbon
geom
obin
an element, first write for aldehydes and ketones in tube,
monoxide, –
N which is a better ligand than N oxygen. Carbon
–
ng the Periodic Table, from Topic 26.2, Reactions of the Some
th nitrogen
2 – atom acting as faulty
2– gas monoxide
heaters. Because
▲
is often
Figureit 7
formed
binds
A more
square
by incomplete
strongly
planar to
complexthecombustionCompin
Cl4] [ Ni ( CN )4 ] carbonyl group in aldehydes and
mplex protein called globin. iron than oxygen, it is possible to suffocate in a room with
en molecule as a ligand. plentiful oxygen.
ketones. Repre
2+ Synoptic link A solu
ration
2 is not a of
very V
good ligand, Repre
is use
in water, for example, copper Anaemia is a condition which may be caused by a diagra
be3.easily
Its given
electron up to cells. You will learn more about Aldeh
omes surrounded by water shortage of haemoglobin. The body suffers from a visual
2(i)
(ii) (i)
TwoName
of the the type of
complexes bonding
formed that
by occurs
copper between
are [Cu(H
Name the type of bonding that occurs between a ligand
2
a
O)ligand
]2+ and
and a
CuCltransition
4 .
2–
6 and a transition
element.
element.
Draw three-dimensional diagrams of their structures in the boxes and name their shapes.
8.76 Skill check
.......................................................................................................................................
....................................................................................................................................... [1] [1]
[Cu(H2O)6]2+ CuCl 42–
3
(ii) (ii)
Which Which
of the offollowing
the following speciesspecies
can actcanas acta as a ligand?
ligand?
Complete
Complete the table
the table by placing
by placing a ticka (tick) in
( the) inappropriate
the appropriate column column to indicate
to indicate whetherwhether
the the
speciesspecies
can actcanas acta as a ligand
ligand or not.or not.
can act
can act cannot
cannot act act
species
species
as a as a ligand
ligand as a as a ligand
ligand
–NO –
NO3 3
BF3 BF3
H2NCH
H2NCH 2 CH 22 CH
NH 22 NH 2
6
26
+NH +
NH4
shape: ..............................................
4 shape: ..............................................
) The cyanate ion, NCO–, can act as a monodentate ligand.
(iii) Platinum forms square-planar complexes, in which all four ligands lie in the same plane as [2] [2]
4(i) State
the Ptwhat
atom.is meant by the terms
There are two isomeric complexes with the formula Pt(NH3)2Cl 2.
8.77 Skill check
Draw the shape of hexacyanoferrate(III) ion, [Fe(CN)6]3—
4
ligand. .................................................................................................................................
8. 78 Skill check
Complex Ions WS 2
.............................................................................................................................................
1(ii) Two of the complexes formed by copper are [Cu(H2O)6]2+ and CuCl 42–.
Draw three-dimensional diagrams of their structures in the boxes and name their shapes.
[Cu(H2O)6]2+ CuCl 42–
shape: .............................................. shape: ..............................................
2
(iii) Platinum forms square-planar complexes, in which all four ligands lie in the same plane as
3 3
CN CN−
Cu 2+
8.79 Skill check H3N NH3

Worked example 2
NH3
State the formula of each of the following complexes.
a b c
H H
Cl −
NH3 Cl − H H
H3N NH3 N N
H H
Cu2+ Co2+ Co3+
H
− H
H3N NH3 Cl Cl− N N
H H
NH3 Cl− Cl−
H H
Solution
c
a The charge on the central ion is 2
H H doesn’t affect the overall charge of
H Cl− H 2
is [Cu(NH3)6] .
N N
H H b The charge on the central ion is 2
Co3+ four ligands have a charge of 4 . O
8.80 Skill check
8.81 Skill check
8.82 Types of Ligands
Most ligands form only one co-ordinate bond with the central metal ion
in a complex.
These ligands are described as monodentate because they have only
‘one tooth’ with which to bind with the central cation. (The word dens in
Latin means ‘tooth’.)
In some cases, ligands can form more than one bond with a metal ion
and these are described as polydentate (or multidentate).
CO CO
H2 H2 O
H2 H2 O O
Monodentate
Monodentate
O
and bidentate
and CO
C C 8. 83 Bidentate Ligands
C CC C C
Most
C
ligands, H Most
O, NH ligands,
, Cl ,−
OH
H O,−
and
NH CN, Cl ,
−−
,f
–O – –
Tetrahedral – Tetrahedral
2 3 2 Trigonal
3 bipyr
NH2 H2N NH2 O O O
with the
(a) Nickel(‘two-toothed’)
Examples of bidentate ligands tetracarbonyl central
(a) Nickelwith
metalthe ion.
tetracarbonyl
which
central
These metal
ligands
form two co-(b) Iron pentac
ion. areT
which literally means
which ‘one
literally means
tooth’. Some ‘one ligan
to
ordinate bonds withFigure
the central cation
6.8 Complexes inofcomplexes
Figure transition
6.8 Complexes are:of and
metals transition
carbonmetals
monoxide.
and
one co-ordinateone bondco-ordinate
with the same bond centra
with t
rms two forms forms
two two forms two
1,2-diaminoethane 1,2-diaminoethane
and the ethanedioateand theione
1,2-diaminoethane,
dinate bonds co-ordinate
co-ordinate H 2NCH 2CH 2NH
bondsbonds co-ordinate bonds 2 ethanedioate, C 2O 42—
bonds with the bonds same central
with thecation
sameand centralare
e 6.9 Bidentate ligands.
Figure 6.9 Bidentate
H2 H2 ligands. O O
H2 H2 Figuretoothed’,
toothed’, 6.9). Monodentate
O
Figure 6.9). Mon
O
C C C CC C C C
The bidentate
–O – ligand
The Most
bidentate
–
ligands,
1,2-diaminoethane
– ligandH Most
O, NH
1,2-dia
2 (ol
H2N NH2 H2N NH2 O O O
context to ‘en’)context with the
uses thetonitrogen centralwith
‘en’) usesatoms meta
the nit th
a
which have a lone which which
pairhave aliterally
of electrons, means
lone pairwhich
toofbin
el
two points. In the one co-ordinate
twocomplex
points. Iniontheshownone
bond
inco
complex F
forms two forms forms
two two forms two
1,2-diaminoethane 1,2-dia
ant
1,2-diaminoethane
co-ordinate bonds co-ordinate
co-ordinate 1,2-diaminoethane
attach to
bondsbonds co-ordinate bondsthe nickel
attach ion
number is 6 and number bonds
the shape
is 6 ofwith
and thethe
the bonds
same
complex
shape
sis
Figure 6.9 Bidentate ligands.

Figure 6.9 Bidentate ligands.
only they form
Cl one dative bond with the central d-block metal ion. A number only one
of larger dative
ligands arebond
Cl
alm two or moresquare Cl
dativeplanar
bonds with the centrallinear able
metal ion and are to to
said form
be two or more dative
polydentate. The
8. 84 Bidentate Ligands
complexes can be very stable and are■known resulting complexesPolydentate
can be ver
Figureas chelates or chelating
13.15 complexes.
ale often known square planar agents. Ethanedioate
as chelating Common linear
ions
shapes and
of ligands are
1,2-diaminoethane often known
moleculesas che
are
One end of the molecule will bond with one of the six bonds of the
ligands, while the negative ion derived from EDTA
complex ions bidentate ligands,
(ethanediaminetetraethanoic while the
acid) is ne
metal ion. The second bond is made 90˚ across thehexadentate,
first bond with any
forming up to six
ate, forming up to six dative bonds per ion (Figure 13.16).
other remaining bonds. The bonds look like teeth hence the word
‘dentate’.
– H2 ■ Figure 13.16
H2 O O – –
O N N O O
H2C H2C C C
2+ 2+ 2+ 2+
M 2+
M M 2+
M M M
H2C H2C C C
– –
–
O – N N O O
H2 H2 O O
1,2-diaminoethane,
anedioate
– b The H 2NCH2CHH
1,2-diamino- 2 2NH2 a O
ethanedioate, O
The C2O4
ethanedioate
– 2—
O OO O ON O O
on acts as a H2C
ethane molecule acts – –
C ion acts as a
(oxalate)
–
C C CO –
O O OC C
occur
occur
on the
on oxygen
the oxygen atomH2atom
N so itso
would
NHit
2 would
be impossible
be impossible for wit
the
fo
(a)
2+ Nickel
2+ tet
one8.
lone
pairspairs
to form
to form
two
85 Bidentate ligands two
coordinate
coordinate
bondsbonds
to the
to Co
the Co, where
,
wh w
Figure 6.8 Compl
onelone
pairspairs
of 1,2-diaminoethane
of 1,2-diaminoethane are separated
are separatedand and
so itsocanoneit
Bidentate ligands only form octahedral complexes. forms two
forms two 1,2
bidentate
bidentate
ligand.
ligand. co-ordinate bonds co-ordinate bonds
bon
FigureCH Bidentate ligands. H H
6.9 CH too
2 2 2 2
CH 2 CH 2 C C
H2 O H2 O H2 N H2 N The
2+ 2+ 2+ 2+ H2N NH2
H2 N H2 N con
wh
Co Co Co Co two
forms two
co-ordinate bonds 1,2 c
num
nalysis
Figure 6.9 Bidentate lig

Figure
Figure
25.7 25.7 ang
–
Cl
– + –
Cl Cu Cl
Bidentate
8.86 Complexes with a Ligands: H2NCH2CH2NH2 complex
co-ordination number
of 2 are usually linear
Cl– Complex formed by the bidentate ligand 1,2-diaminoethane with
nickel(ii) ions. Note the use of ‘en’ as an abbreviation for the ligand.
2+ 2+
H2N CH2
en
2+ CH2
H2
en N NH2
pair of electrons to form a co-ordinate bond
hese ligands are described
H2C as monodentate
2+ 2+
Ni
oth’ to hold onto the central cation (dens is en Ni
monodentate
+ ligands include H2O, NH3,
H2C
N NH2
H2
ne lone pair of electrons that can form co-
etal ion. Bidentate (‘two-toothed’) ligands, CH2 en
valent bonds with metal ions in complexes.
H2N CH2
en
2-diaminoethane, H2NCH2CH2NH2, the
Figure 15.16 Representations of a complex formed by the bidentate ligand
mino acids (Figure 15.16).
ons
of a complex ion with optical isomers is [Ni(H2NCH2CH2NH2)3] , 2+
8.87 Bidentate Ligands: H2NCH2CH2NH2 complex
ure 6.17
Complex formed by the bidentate ligand 1,2-diaminoethane with
nickel(ii) ions. Note the use of ‘en’ as an abbreviation for the ligand.
en
The ligand
H2NCH2CH2NH2
2+
is represented
Ni as
en
en
en
en
imaginary
(cis-isomer) (trans-isomer) (tr
only occur with a multi-dentate ligand for example 1,2-diaminoeth
H NCH
Figure CH
6.14
8.882 Bidentate
2
NH .
Cis–trans
2
Each
(E/Z)of the
isomersNH groups has a lone
of diamminedichloronickel(
2 ligand complexes 2
pair
II) andof electro
tetraammi
they can approach the central metal ion in a vertical plane or a ho
The shape(Figure
plane of a complex In Figure 6.14, consider
6.15). ion showing M surrounded by three molecules the bo
of a bidentate ligand and the central metal ion.
● If This ligand is in the
the Cl –(metal ion)–Cl
− −
b
horizontal plane.
These two ligands ● If the Cl –(metal ion)–Cl b
− −
are in the vertical
plane, but twisted at
results.
90º to each other. M
Optical isomerism
Octahedral complexes can als
analysis
non-superimposable mirror im
only occur with a multi-denta
Figure 6.15 The shape of a complex ion showing M surrounded by
H NCH CH NH . Each of the N
one with a smaller charge, so the
This increases the repulsion betw
8.89 Bidentate &13.1 mondentate
First-row d-block ligand elements complexes467
ligand and the d-orbital electrons
CHEM COMPLEMENT
agents are usually much more stable than those formed 2 the size of the ligand. Smaller liga
rmed the chelate effect,CH and is due to an increase in CH
increasing the repulsion between
Optical
g a bidentate isomerism 2 2
Cl
H2C NH2 H2N CH2 electrons and increa
and d-orbital
lexes that areto exhibiting geometric isomerism,
In addition amount NH 2 of splitting Clfor some comm
[Ni(NH ) ]2+ (aq) + 6H O(l) K =— 4.0 × 10
8
igure 13.24).
3 6
bidentate ligands H2N 2
such as 1,2-diaminoethane CH 2
Br Br NH2
Ni(en) ]3+
enantiomers.(aq) + 6H O(l) K = 2.0 × 1018 Cl H 2 O Co 3+NH3 CN 13.2
(ethylenediamine)
3 2 and the ethanedioate
Co ++
3
Co +
CH and
d optical
(oxalate) ion can show another type of For
2
example, the chromium (III) ion, C
and, 1,2-diaminoethane, H N H 2 N–(CH )
2Br
2 –NH
—
.
2Br NH NH 2
se the
ed light
f a(see
two
complexin
13.2 Coloured complexes
stereoisomerism, known as optical isomerism However, when the ion is surrounded
section 9.7). ion
2
Optical isomers can be

NH 2 2
H2N – d-orbitals have the

isolated atom, split into three orbitals CHof lower energ
H2C NH2 but split into twoHsub-levels N CH in2 a complex ion; the elec
CH
2
identified
e the concentrationsbecause their
of solutions
chemicals can
that rotate
are themselves 2 2
may cause CH2the d-orbitals in complex When white
ions
CH to light
split sofalls
that on
the the comple
energy o
plane-polarized
dtheory
substance during light
a (see
chemical p. 327).
reaction (Chapter 6). By 2
transition between them lower
corresponds
Figure energy
to
3.3.7 a
The photon
two d orbitals
optical of are
visible
isomers of excited
light
cis[Co(en) Cl t
]
thatThetake
twoplace in
different [Co(en)
reactions
optical 2Br2] rotate
involving
isomers
+
the formation
light of [Co(en) 2 Cl 2]+ 2 2
Figure
f a solution appears to be a blue-green
■ 13.24 The enantiomers of of energy
cis-[Co(en) 2 absorbed
Br 2]+,
depends on the d
canin be used todirections.
opposite determine the
The formulas
complex is of these complex 700 nm 400 nm
■ The colours of complex
where en represents 1,2-diaminoethane Theions remaining wavelengths of the li
apeutic effect, trans- or E-isomer (bottom)
23
QUESTION
The transition metals
8.90 Bidentate & mondentate ligand complexes
5 a Cobalt forms a complex with the simplified
structure:
2+ 2+
en + NH2 +
en en
rror images
Br of each
— Cl H2N CI Cl
whenen
there are
Ni two or 2+ Cr Cr
CO
— Cl en H2N CICl
Br en
complexes arounden NH2
mirror
he same position as the curve represents CH2 CH2
positions Ni(en)
of 2Br2 en
the en is an abbreviation for
ormed by the bidentate ligand i Give the co-ordination number in this complex
ethane-1,2-diamine:
bout this is to use
he use of ‘en’ as an abbreviation for the ligand.
ii Draw the stereoisomer of this complex.
is particularly impressive because it
(ii) There are three isomeric complex ions with the formula [Cr(en)2Cl 2] .
Complete the three-dimensional diagrams of the isomers in the boxes
Complete the three-dimensional diagrams of the isomers in the boxes.
8.91 [Cr(en) Cl ]
2 You +
Complete the three-dimensional diagrams of the isomers in the boxes
2 may use to represent en.
You may use NN N to represent en.
You may use N N to represent en.
N
Cr Cr
Cr
Cr Cr
Cr
H2N CH2
Chapter 6 Transitio
8.92 Hexadentate ligands H C
Figure 6.11 The walrus, the tiger and the crab could perh
2
Figure 6.10 A nickel complex with three molecules of
A few ligands, such as EDTA (ethanediaminetetraethanoate), are
N
particularly strong because they can form six co-ordinate bonds with
H2
the central metal ion in complexes.
–
OOCCH2 CH2COO
– Polyden
One of t
H2N
NCH2CH2N of attach
– – Figure 6.
Figure 6.10 A nickel complex
OOCCH2 CH2COO
124 Each of t
Figure 6.12 The EDTA ion.
EDTA 4−
therefore
= 8.93 Hexadentate ligands
O
H
O
− −
= = O
− C − C H 2NCH2CH2NH2 H−C−C –
=
− – − O−
O
The [EDTA] ion bound to
4— a central−metal O H
ion in an octahedral O= C−
N CH
– −C −
−
coordination complex. H H O CH −
−
2
ethanedioate 1,2-diaminoethane glycine 2+
–
Cu
O− C
−
N − CH2
C − CH −
O= O
−
2
=
C − CH2 CH2 − C = CH2
– − – O –
O
−
−
−
O
−
O −
NCH2CH2N C
O
=
O=
−
−
C − CH2 CH2 − C = O
– − –
−
O O
Fig 25.14 The complex ion formed by
EDTA
with a Cu2+ ion. EDTA binds cations s
Three bidentate ligands and the hexadentate ligand EDTA strongly that it can be used sparingly
antidote to lead poisoning by trapping
ions. It is also used as a means of ext
ands, such as EDTA (ethanediaminetetraethanoate), are particularly the shelf life of manufactured foods, s
cause they can form six co-ordinate bonds with the central metal salad dressings, by trapping metal ion
mplexes. EDTA binds so strongly with metal ions that it makes them would catalyse the oxidation of veget
ids (Figure
xtremely 15.16).
pure nickel (Mond process). benzene.
1,2-diaminoethane with nickel(ii) ions. Note the use of ‘en’ as an abbreviation It is also
for charge used
the ligand. as a preservative in foods
Deduce the on the tetraamminedichlorochrom
ucing the total charge given the formula of the ion and ligands therapypresent
to remove harmful heavy metals or thei
e ligand. 8.94 Hexadentate ligands - EDTA
The hexadentate ligand EDTA
otal or net charge on a complex depends upon the The
■4−Figure 13.17
numberis
sodium
particularly
of ligands, impressive
salt of their charge
The because
formula
and the has it
two chloride ions, Cl −, and four am
can form six co-ordinate bonds with the central metal iontwoinnegative charges (−2). The central chromium c
complexes.
ion state of the central transition metal ion to which 10
EDTAthe ligands
Deduce the are bonded. The total
ause it 4− is the common abbreviation for charge
this
contributes three positive charges (+3). Hence – the
EDTA can
charge on a complex be deduced O from its composition
total and ion,
the which binds
oxidation
and state so
of firmly
the with
formula is therefore [CrCl O (NH ) ]+. O
plexes. metal ions that it holds them in solution and makes them chemically inactive.
2 3 4
–
l cation. The oxidation state–
of the central ion can2–be deduced
formulas offrom
the the formula and charge– O 2
ly with
complex. O C 829055_13_IB_Chemistry_451-488.indd 463
following complex
Figure 15.17 shows how the hexadentate ligand can fold itself around metal Deduce the O
oxidation stateCof copper in the [Cu(CN)
C CH4]2
nactive. O such as Pb , so that
ions, 2+ CHfour
2 oxygen
ions: a nickel(II) ion
atoms and two nitrogenO atoms form
–O
CH2
with six ammonia C CH
d metal C
co-ordinate CH2
bonds to the
The complex ion
4− is an2 anion with a total or net cha
ked example –O N metal ion. This ligands,is and
theaion formed when – as EDTA is
O ligands which contribute N a total of four negative
ms form used to treat lead poisoning. The EDTAcopper(4− II) ion
ion forms
with such a stable complex Pb 2+
4− CH
13/04/19 10:03 PM contribute one positive charge CHso its
2
oxidation stat
TA is
ce the charge on the tetraamminedichlorochromium(
2+
2 III) complex ion. What is its formula?
with Pb ions2+that they can be excreted through the kidneys.four chloride ions.
2+
omplex Pb − 11 Find about the Cu
he formula has two chloride ions, Cl , and four ammonia 4− molecules, NH3, so the ligands contribute
The disodium salt of
wo negative charges (−2). The central chromium cation
EDTA CH is added
mechanism to commercially
of produced salad
so itIsomerism in complex
–
O CH2 ions
2 has an oxidation number of +3,■
dressings to extend their shelf life. The EDTA
action of 4− ion
cisplatin
ntributes three positive charges (+3). Hence the total or net charge on the complex ion is +1. The traps traces of metal ions C H
drmula
salad –
that[CrCl
O
is therefore would(NH )otherwise
] +. N
catalyse the and
oxidationoutline
of any
vegetable –
oils.
O The disodium O N
tal ions C
2 3 4
H C changes that occur Cis–trans C
isomerism H C
–
O
salt of EDTA4− is also an 3−ingredienttoof
2
the bathroom
complex ion cleaners
Where
to a
help remove
complex ion
2
contains two different ligan
sodium
ce the oxidation O state of copper in the [Cu(CN)
2+ CH
4] 2 complex ion. What is its name? O CH 2
scale by dissolving
–
O Ca
C ions from the calcium
during its use carbonate
as an left
differentby hard – water.
O
arrangements Cthe ligands (Figure 13.22
of
remove anti-cancer agent. Figure 15.17 The comple
he complex ion is an anion with a total or net charge of −3. The formula has four cyanide
water.which contribute the relative
ions actingpositions of the two ligands. Cis mean
ligands Tip a total of fourOnegative charges (−4). Hence the central copper ion must
of isomerism is only possible for complex ions
O
with the EDTA 4− ion with a Pb
ntribute oneFigure
positive15.17
chargeThe
so complex ion state
its oxidation formed byThis ion is the tetracyanocuprate(
is +1. I) ion. 13.18 The [Cu(EDTA)]2− complex
■ Figure
[Pb(EDTA)]
the EDTA crystals
4− consist
ion with 2+ 2— The cis [Cu(EDTA)]
complex
the disodium salt of ethylenediaminetetraacetic acid. Chemists
a Pb of ion.
[PtCl2(NH )
2—
3 2], systematic name c
cisplatin (Figure
− 13.23) and is used in chemotherap
sometimes use the abbreviation Na2H2Y for the salt, where Y represents the 4 ion.
emists isomer, known as transplatin, has no anti-cancer p
8.95 Types of Ligands
Ligands are of three types that have three different coordination
numbers.
• Monodentate ligand forms one dative covalent (co-ordinate) bond
with a central metal ion in a complex.
• Bidentate ligand forms two dative covalent (co-ordinate) bonds with
a central metal ion in a complex.
• Hexadentate ligand forms 6 dative covalent (co-ordinate) bonds with
a central metal ion in a complex.
• Multidentate/polydentate ligand forms more than one co-ordinate
bond with the same metal ion.
gold(I), form linear complexes with ligands. The structure.
co-ordination number in these complexes is 2
(Figure 24.7). Table 24.4 shows some common ligands.
8.96 Ligands
Name of ligand Formula Example of Co-ordination Shape of complex
complex number
water H2O [Fe(H2O)6]2+ 6 octahedral (see Figure 24.4)
ammonia NH3 [Co(NH3)6]3+ 6 octahedral
chloride ion Cl– [CuCl4]2– 4 tetrahedral (see Figure 24.5b)
cyanide ion CN– [Ni(CN)4]2– 4 square planar

(see Figure 24.5a)
hydroxide ion OH– [Cr(OH)6]3– 6 octahedral
thiocyanate ion SCN– [FeSCN]2+ or

[Fe(SCN)(H2O)5]2+ 6 octahedral
ethanedioate ion (abbreviated as –OOC COO– [Mn(ox)3]3– 6 octahedral

‘ox’ in the formulae of complexes)
1,2-diaminoethane NH2CH2CH2NH2 [Co(en)3]3+ 6 octahedral (see Figure 24.6)

(abbreviated as ‘en’ in the formulae
of complexes)
8.97 Skill check
What is the oxidation number of the transition metal in each of the
following complexes?
i [Co(NH3)6 ] 3+
ii [Ni(CN)4]2–
iii [Cr(OH)6] 3–
iv [Co(en)3] 3+
v Cu(OH)2(H2O)4
8.98 Complex ions
A simple formula does not make it clear which groups are attached to
the metal ion, it is common practice to enclose the complex ion in
square brackets.
An example of this is Cr(H2O)6Cl3, which does not make it clear which

ligands are attached to the chromium ion.
It could, for example, be [Cr(H2O)6]Cl3 (which has no chlorine ligands

but has three free chloride ions) or
[Cr(H2O)5Cl]Cl2.H2O (which has one chlorine ligand and two free

chloride ions).
8.99 Stereoisomerism in complexes
Because of the three-dimensional shape of complex ions and the
positions of ligands around the central metal ion, isomers can occur in
four co-ordinated and six co-ordinated complexes.
Isomers are compounds with the same formula, but different

arrangements of their constituent atoms.
Transition metal complexes can form both geometrical isomers (cis-

trans) and optical isomers.
Pb ions that it can be excreted through
2+ result of the spatial
+ positio
[Co(NH3)4Cl2] give rise to c
the kidneys.
8.100 Stereoisomerism in complexes co-ordinated complex ions
stereoisomerism defines co
Square planar complexesDiamminedichloronickel(
can exhibit cis-trans IIisomerism.
)
tructural formula,Clbut
– have a different arrangement
–
the
in trans-form
space.
Cl H
merism falls into one of two categories:
NH3 NH3
2+ 2+
Ni Ni
ns (E/Z) isomerism
Cl–
H3N H3N
–
NH3 Cl
isomerism.the cis-form
ns (E/Z) isomerism
Z-isomer E-isomer
e planar (cis-isomer)
structure of [Ni(NH ) Cl ] and the (trans-isomer)
octahedral structure of
3 2 2
–trans (E/Z) isomerism
Z-isomer E-isomer E-is
square planar (cis-isomer)
structure of [Ni(NH
) Cl ] and the (trans-isomer)
octahedral structure
of (trans
8. 101
+ Stereoisomerism
NH3)4Cl2] giveFigure
rise to cis–trans
6.14
3 2 2 in complexes
Cis–trans(E/Z)
(E/Z) isomerism (Figure 6.14).
isomers of diamminedichloronickel(II) and tetraammined
Octahedral complexes can exhibit cis-trans isomerism with

In Figure 6.14, consider the bond
monodentate ligands orTetraamminedichlorocobalt(
optical isomerism with )
IIIand bidentate ligands.
the central metal ion.
– –
Cl ●ClIf the Cl –(metal ion)–Cl bon
− −
the trans-form
H 3N H3N ● If the Cl –(metal ion)–Cl bon
− −
NH3 NH3 results. NH3

3+ 3+
Co Co
H3N H3N
Cl–
NH3 Optical
Cl isomerism
–
the cis-form Octahedral complexes can also f

–
Cl
e analysis
NH3
non-superimposable mirror imag
mer E-isomer only occur with a multi-dentate
Z-isomer
omer) (trans-isomer) (cis-isomer)
H2NCH2CH2NH2. Each of the NH
8.102 Square planar: cis-trans isomerism
For a complex with two ligands of one type and two of another type in
the square plane, like platin, Pt(NH3)2Cl2, there are two different
arrangements possible of these ligands around the central ion.
Stereoisom
Cl NH3 Some complex
H3N Pt Cl Cl Pt Cl Square planar
NH3 NH3 Octahedral co
the cis-form the trans-form or optical isom
the ‘cis’ form the ‘trans’ form
Z isomer E isomer E-Z isomeris

8.103 Square planar: cis-trans isomerism
The two structures are isomers because they are non-superimposable.
The terms cis and trans are used in the same way as they are in
organic chemistry.
Trans implies ‘opposite’ – notice that the ammonia molecules are

arranged opposite each other in that version, and so are the chloride
ions.
Cis implies ‘on the same side’ – in this instance that just means that the
ammonia molecules and the chloride ions are next to each other.
cis isomer, the like ligands are in adjacent positions. In the sec
isomer, the trans isomer, the like ligands are diagonally oppos
8.104 Properties of cis-trans isomers
Biological systems are often sensitive to the difference betwee
isomers. A well-known example of this is the geometric
A pair of geometrical isomers will have different chemical properties. isomer
chemotherapy drug. Its trans isomer, transplatin, does not wo
For example,way at all. is one of the most successful anti-cancer drugs
cisplatin
whilst the trans-isomer has no therapeutic effect.
H2O
Cl NH3 H3N Cl H2O
Pt2+ 2+
Pt C
Cl NH3 Cl NH3 H2O

cisplatin transplatin H2O
c
A DEFINITION
his name comes from the Greek
Trans-form
Bligand forms a A ligands on A chelate is a complex ion in
mplexes8.105 Octahedral:
the cis-trans
B opposite isomerism
sides which each ligand forms two or
M of M, at 180° more co-ordinate bonds
BOctahedral complexes of the type MA2B4 also exhibit cis–trans with the
erful than simpleB monodentate central metal ion.
isomerism.
nced by chelation
A as the
d the central metal ion more
A
he others still hold the metal
Cis-form A
B Trans-form
A ligands on A B A ligands on
same side of B opposite sides
M M
M, at 90° of M, at 180°
mplex ions B B
B B
mplex ions and the positions B A
ers can occur in four
Fig 25.15 Isomers of complexes of the type
. MA
Isomers
B are compounds with A
2 4
Cis-form
s of their constituent atoms B
A ligands on
of isomerism occurs in octahedral and
th different arrangements +
nar complexes. Take the octahedral OH2
complexes
8. 106 can form
Octahedral:
+
both cis-trans
− isomerism
H 2 O of [CrCl2(H
OH 2 2O)4]
+
on [CrCl2(H2O)4] . The Cl ligands
mers) and optical isomers. Cr
xt toTake
each other (the cis- or Z- form)
the octahedral complex ion [CrCl2(H2O)4] . The Cl ligands may be
+ —
ositenext
sides
to of
eachtheother
central chromium
(the cis-form) Cl sides of theClcentral
or on opposite
OH2
ans- or E-form)
chromium
ce relative to ion(Figure
one (the 9).
trans-form).
another.
al and
are planar complex OH2
platin, the+ OH2 +
dral
s may be nextH2O to each other OH2 (the cis- Cl OH2
nds
) or on opposite sides Cr of the central Cr
orm)
ion (the trans- or E-form). A pair of H O Cl
um Cl Cl 2
al isomers will have OHdifferent
2 chemical OH 2
For example, cisplatin is one of the ▲ Figure 9 The cis- or
the cis-form the trans-form
essful anti-cancer drugs OH2
whilst + the Z-isomer (top) and the
er has no therapeutic
Cl effect,
8.107 Octahedral: cis-trans isomerism of [Co(NH ) Cl
34 2 ]+
The left-hand isomer is the cis isomer as the two Cl− ligands are beside
each other, i.e. at 90° to each other. The right-hand isomer is the trans
isomer as the two Cl− ligands are opposite each other, i.e. at 180° to
each other.
+ +
Cl Cl
H3N Cl H3N NH3
Co Co
H3N NH3 H3N NH3
NH3 Cl
the cis-form the trans-form
cis isomer trans isomer
2 6
complexes.
8.
CLES 2016
108 Skill check
[V(H O) ] + 3+
2Cl – [V(H2O)4Cl 2]+
9701/41/M/J/16 + 2H2O [Turn ove
2 6
Complete the three-dimensional diagrams to show the two isomers of [V(H2O)4Cl 2]+.
Hameed Transition Elements W
V V
isomer 1 isomer 2
[2]
(ii) State the type of isomerism shown by isomer 1 and isomer 2 in (i).
8.109 Optical isomerism
In transition metal complexes optical isomerism occurs when there are
two or more bidentate ligands in an octahedral complex.
The transition metals
23
The two isomers are non-superimposable mirror images of each other.
+ +
en en
r images of each Cl Cl
n there are two or Cr Cr
Cl Cl
en en
mplexes around
mirror
same position as
ositions of the en en is an abbreviation for
ons
An example of a complex ion with optical isomers is [Ni(H2NCH2CH2NH2)3] , 2+
8.110 Optical isomerism

shown in Figure 6.17 of [Ni(H2NCH2CH2NH2)3] 2+
en
en
The ligand
H2NCH2CH2NH2
is represented
en 2+
Ni Ni 2+
as
en
en
en en
en
imaginary
mirror
Figure 6.17 Optical isomers of [Ni(H2NCH2CH2NH2)3] . 2+
non-superimposable mirror images of each other. Optical isomeri
Chapter 6 Transition elements and qualitative analy

only occur with a multi-dentate ligand for example 1,2-diaminoe
Figure 6.15 The shape of a complex ion showing M surrounded by of the NH groups has a lone pair of electr
8.111 Optical isomerism in complex ions three molecules of a bidentate ligand.
H2NCH 2
CH 2
NH2
. Each 2
they can approach the central metal ion in a vertical plane or a h
plane (Figure 6.15).
This gives rise to two possible isomers (Figure 6.16).
Optical isomers of a complex formed by three molecules of a bidentate
This ligand is in the
ligand: These two ligands
horizontal plane.
Chemistry of complex ion

are in the vertical
plane, but twisted at
90º to each other. M
M Figure 6.15 The shape of a complexM ion showing M surrounded by

three molecules of a bidentate ligand.
This gives rise to two possible isomers (Figure 6.16).
Figure 6.16 Optical isomers of a complex formed by three molecules of a bidentate ligand.
126
8.112 Optical isomerism in complex ions
Optical isomers are said to be chiral.
They have identical chemical properties but can be distinguished by

their effect on polarised light.
One isomer will rotate the plane of polarisation of polarised light

clockwise and the other anticlockwise.
the left) and ‘
the d and l forms based on a
8.113 Optical diagram. This would
isomerism be carried
in complex ions Octahedral co
out practically by determining the isomers. It is
Here are the two optical isomers
effect of 3+ formed when 1,2-diaminoethane
each on plane polarised octahedral
forms a complex with Co ions. The two optical isomers have a sh
light.
different three-dimensional spatial arrangement of the ligands A
around
racemic mi
be equal conc
H2N
3+
H2N
3+ other out.
H2N NH2 H2N NH2
Co Co
Figure 25.22
H2N NH2 H2N NH2 forms a comp
H2N H2N NH2. The two
arrangement
Figure 25.22
H 2C CH2
H2C H2NH
N 2H2C NH22
NH H2N Br
H
CH2 2 N Br
CH2
H2N NH2
CH2 CH2
8.114 Optical isomerism in complex
H C NH
ions Br CH2 CH2
H2N CH2
2 2
H2C CH2
b b 2+ 2+ 2+ 2+
en
trans form en en cis form
en
2+
Ni also forms Ni en with
a complex en en
Ni three 1,2-diaminoethane
Ni en Ni ligands. This has only the cis
form as the distance is too large for the ligand to stretch across the trans positions.
The cis form
en can also be resolved into optical
en isomers (see Figure
en 24.13).
en
9omerism
The in the
two non-superimposable
Figure 24.9 The two 24_12 optical
H2C
Cam/Chem isomers
non-superimposable
AS&A2 of Ni(NH
optical CH
isomers
2 2 CH
of
2 NH )
Ni(NH 2+: a the full structure;
2 3 2 CH 2 CH2 NH 2 )3
2+
CH: a
2 theb a
full simplified
structure; structure
b a simplified
on NH H N
presenting
with ‘en’a representing
molecule of 1,2-diaminoethane.
aHmolecule
2C of 1,2-diaminoethane.
2 2 CH2
Barking Dog Art
H 2N NH2 CH2 H2C H2N NH2
Ni Ni
CH2 H2C
NH2 H 2N
H2N NH2
H 2C NH2 H2N CH2

H2C CH2
the left) and ‘
the d and l forms based on a
8.115 Optical diagram. This would
isomerism be carried
in complex ions Octahedral co
out practically by determining the isomers. It is
Here are the two optical isomers
effect of 3+ formed when 1,2-diaminoethane
each on plane polarised octahedral
forms a complex with Co ions. The two optical isomers have a sh
light.
different three-dimensional spatial arrangement of the ligands A
around
racemic mi
be equal conc
H2N
3+
H2N
3+ other out.
H2N NH2 H2N NH2
Co Co
Figure 25.22
H2N NH2 H2N NH2 forms a comp
H2N H2N NH2. The two
arrangement
Figure 25.22
8.116 Optical isomerism in cis-[Co(en)2Br2]+
Optical isomers of a complex formed by two molecules of a bidentate

13.1 First-row d-block elements 467
ligand and two ions of a monodentate ligand, e.g. cis-[Co(en)2Br2]+
ating agents are usually much more stable than those formed
s is termed the chelate effect,CH and2
is due to an increase in CH 2
aining a bidentate H2C NH2 H2N CH2
complexes that are
q) ! [Ni(NH 2+ 8
her (Figure 3)6] (aq)H+N6H2O(l)
13.24). K = 4.0 × 10
Br Br NH2
2
)wn!as[Ni(en) ]3+(aq)
enantiomers.
3 + 6H 2O(l) + K = 2.0 × 1018
+
13.
Co Co
s called optical
ate ligand, 1,2-diaminoethane,
H N H 2 N–(CH 2)
Br2 –NH 2.
Br NH
because the two
olarized light in
la of a complexisolated
13.2 Coloured complexes
2
ion
2
– d-orbitals have the
ions. H 2
C atom,
NH but split into two H sub-levels
N CHin2
a complex ion; the ele
measure the concentrations of
may cause chemicals 2
that are themselves
CH2the d-orbitals in complex ions
2
CHto split so that the energy
loured
(VB) theorysubstance during a chemical reaction (Chapter 6). By 2
transition between them corresponds to a photon of visible light
8.117 Optical isomerism in cis-octahedral complexes
on Compounds
oordination Compounds
What is also interesting to note is that in an octahedral molecule that
has two bidentate ligands, and two other similar ligands, can not only
ck
ge.to
exhibit cis-trans
see ifto see if
Check
isomerism but it’s cis-form can also exhibit optical
Mirror Mirror
ne isomerism.
er 180°.
isomer 180°.
The trans molecule of such an ion, however, will not exhibit optical
isomerism. Cis Cis
+ + + +
en en en en
Cl Cl Cl Cl
Co Co Co Co
Cl Cl Cl Cl
en en en en
Nonsuperimposable
Nonsuperimposable
Ligand exchange reactions
8.118 Ligand exchange reactions
In Section
A ligand 7.16 we noticed
exchange that is
reaction acid–base reactions
a reversible reactioninvolve
in whichcompetitions
one ligand
+
between different bases for H ions. In a similar
tries to replace the existing ligand in a complex ion. fashion, complexing reactions
involve competitions between different ligands for metal ions. This results in
reactions in which
For example, metal
when ionshydroxide
sodium exchangesolution
one ligand for another.
is added to aqueous copper(II)
sulfate, hydroxide ions displace water molecules from hydrated
For example, when sodium hydroxide solution is added to aqueous copper(II) copper(II)
ions forming a pale blue precipitate of copper(II) hydroxide. In effect,
sulfate, hydroxide ions displace water molecules from hydrated copper(II) ions this is an
uncharged
forming a paleinsoluble complex.of copper(II) hydroxide. In effect, this is an
blue precipitate
uncharged insoluble complex.
2+ –
[Cu(H2O)6] (aq) + 2OH (aq) → [Cu(H2O)4(OH)2](s) + 2H2O(l)
pale blue soln pale blue ppt
NOTE
The reaction forming the pale blue precipitate of copper(II) hydroxide is
ulfate, hydroxide ions displace water molecules from hydrated copper(II) ions
orming a pale blue precipitate of copper( II) hydroxide. In 2+
8.119 Ligand exchange reaction of Cu with NaOH effect, this is an
ncharged insoluble complex.
2+ –
\
NOTEThe above reaction forming the pale blue precipitate of copper(ii)
The reaction forming the pale blue precipitate
hydroxide is usually simplified to: of copper(II) hydroxide is
usually simplified to:
2+ Cu2+(aq) + 2OH— (aq) → Cu(OH)2 (s)
–
Cu (aq) + 2OH (aq) → Cu(OH)2(s)
excess ammonia solution is now added, the pale blue precipitate dissolves
2+
s water molecules and hydroxide ions around the Cu ion are exchanged
or ammonia molecules. A deep blue solution of tetraamminecopper(II) ions is
roduced:
2+ –
Cu(H O) (OH) ](s) + 4NH (aq) → [Cu(NH ) (H O) ] (aq) + 2OH (aq) + 2H O(l)
8.120 Cu2+ with NH3
When excess concentrated ammonia solution is added to pale blue
copper(II) sulfate solution, ammonia molecules are exchanged for water
molecules around the central Cu2+ ion and the colour changes to a
deep blue.
[Cu(H2O)6]2+(aq) + 4NH3 (aq) ⇌ [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O (l)

pale blue solution deep blue solution
n Section 7.16 we noticed that acid–base reactions involve competitions
8. 121 Cu 2+ with NH
+ 3
etween different bases for H ions. In a similar fashion, complexing reactions
nvolve competitions between different ligands for metal ions. This results in
The reaction takes place in two stages.
eactions in which metal ions exchange one ligand for another.
At first the
or example, alkaline
when solution
sodium of ammonia
hydroxide solution removes protons
is added from copper(
to aqueous the II)
ulfate, hydroxide
hydrated ions displace
copper(ii) ions to water
give amolecules from hydrated
pale blue precipitate of thecopper( II) ions
hydrated
orming a pale
hydroxide. blue precipitate of copper( II) hydroxide. In effect, this is an
ncharged insoluble complex.
2+ –
NOTE
The reaction forming the pale blue precipitate of copper(II) hydroxide is
usually simplified to:
2+ –
Cu (aq) + 2OH (aq) → Cu(OH) (s)
copper(ii) ions to give a pale blue precipitate of the hydrated hydroxide.
8. 122 Cu
[Cu(H2O)6 with NH
2+
2+−
] (aq)
+ 2OH (aq)
3 ! [Cu(H2O)4(OH)2](s) + 2H2O(l)
pale blue solution pale blue precipitate
Then the ligand exchange takes place as the precipitate redissolves to
Then the ligand exchange takes place as the precipitate redissolves to give
give the deep blue solution.
the deep blue solution.
[Cu(H2O)4(OH)2](s) + 4NH3(aq)
pale blue precipitate
2+
! [Cu(NH3)4(H2O)2] (aq) + 2H2O(l) + 2OH (aq) −
deep blue solution

The ligands NH3 and H2O are both uncharged and similar in size. This
The ligands
allows exchangeNHreactions
3 and H2O are both
between uncharged
these ligands and similar
without in size.inThis
a change co-
allows exchange
ordination number ofreactions
the metalbetween
ion. these ligands without a change in
A co- ordination
ligand exchangenumber
reactionofalso
theoccurs
metal when
ion. concentrated hydrochloric acid
is added to copper(ii) sulfate solution. This time, the colour changes from
−
pale blue to yellow as Cl ions replace water molecules around the Cu ion. 2+ Tip
8.123 Cu2+ with NH3
The overall change is a ligand exchange reaction and is a reversible
reaction.
[Cu(H2O)6]2+(aq) + 4NH3(aq) ⇌ [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O(l)
This is a reversible reaction and if the dark blue complex

[Cu(NH3)4(H2O)2]2+ is diluted, the pale blue colour of the [Cu(H2O)6]2+ ion
is restored.
2+ 2
Cu(H2O)6 (aq) + 4NH3(aq) → [Cu(NH3)4(H2O)2]
8.124 Cu with NH3
2+
This is a reversible reaction and if the purple complex [C
There is competition between the H2O and NH3 molecules to attach 2+
is diluted, the pale blue colour of the [Cu(H2O)6] (aq)] io
themselves to the copper ion.
competition between the H2O and NH3 molecules to atta
We have anion. We have
equilibrium withan equilibrium
a constant given with
by theaexpression:
constant given by the
2+ 4
[[Cu(NH3)4(H2O)2] ][H2O]
K= 2+ 4
[Cu(H2O)6] [NH3]
As [H2O] is in large excess and virtually a constant, we ca

equilibrium constant and write:
2+
2+
! [Cu(NH3)4(H2O)2] (aq) + 2H2O(l) + −
2OH (a
8.125 Cu2+ with Cl— deep blue solution
The ligands NH3 and H2O are both uncharged and similar in size. Th
A ligand exchange
allows exchangereaction alsobetween
reactions occurs whentheseconcentrated
ligands without a change in c
hydrochloric acid
ordination is added
number to copper(ii)
of the metal ion.sulfate solution.
A ligand exchange reaction also occurs when concentrated hydrochloric ac
This time, the colour changes from pale blue to yellow as Cl− ions
is added to copper(ii) sulfate solution. This time, the colour changes fro
replace water molecules around
− the Cu 2+ ion.
pale blue to yellow as Cl ions replace water molecules around the Cu io 2+
[Cu(H2O)6 2+
] (aq) + −
4Cl (aq)! [CuCl4 2−
] (aq)
+ 6H2O(l)
pale blue yellow
In this case, however, the ligand exchange involves a change in co-ordinati
This ligand exchange involves a change in co-ordination number.
number. Chloride ions are larger than water molecules, so fewer chlori
Chloride ions are larger than water molecules,
2+ so fewer chloride ions
ions can fit round the central Cu ion.
can fit round the central Cu2+ ion.
8.126 Ligand exchange reaction of Co2+ with NaOH
The simplest ion that cobalt forms in solution is the pink, [Co(H2O)6]2+
When sodium hydroxide solution is added to aqueous cobalt(II) ions,

hydroxide ions displace water molecules from hydrated cobalt(II) ions
forming a precipitate of cobalt (II) hydroxide.
[Co(H2O)6] (aq)
2+ + 2OH (aq)
— → [Co(H2O)4(OH)2](s) + 2H2O(l)
pink solution blue ppt.
We see a blue precipitate of cobalt(II) hydroxide forming, which turns

pink/red when warmed if the alkali is in excess.
8.127 Co2+ with NH3
When excess concentrated ammonia solution is added to pink cobalt(II)
solution, [Co(H2O)6]2+, six ammonia molecules are exchanged for all six
water molecules around the central Co2+ ion.
[Co(H2O)6]2+ (aq) + 6NH3 (aq) ⇌ [Co(NH3)6]2+ (aq) + 6H2O (l)

pink solution brown solution
The pink solution turns brown.

8.128 Co2+ with Cl—
A ligand exchange reaction also occurs when concentrated

hydrochloric acid is added to cobalt(II) sulfate solution.
This time, the colour of the solution changes from pink to blue as Cl−
ions replace water molecules around the Co ion.
2+
[Co(H2O)6]2+ (aq) + 4Cl— (aq) ⇌ [CoCl4]2— (aq) + 6H2O (aq)

pink solution blue solution
8.129 Stability constant/Kstab
If Kc is divided by the concentration of water molecules in the ligand
exchange reaction, we get Kstab.
[CuH2O)6]2+ + 4Cl- ⇌ [CuCl4]2- + 6H2O
([CuCl4]2-)(H2O)6
Kc =
([CuH2O)6]2+)(Cl-)4
Kc ([CuCl4] )
2-
= = Kstab
(H2O)6 ([CuH2O)6]2+)(Cl-)4
8.130 Relative stability of complex ions
In aqueous solution, the simple compounds of most transition metals
contain complex ions with formulae such as [Cu(H2O)6]2+ and
[Co(H2O)6]2+.
When solutions containing other ligands, such asCl ,

— are added to
aqueous solutions of these hydrated cations, the mixture comes to an
equilibrium in which the water molecules of some complexes have
been replaced by the added ligands.
For example, the equilibrium which results when concentrated sodium
chloride solution is added to aqueous cobalt(ii) ions is:
[Co(H2O)6]2+ (aq) + 4Cl— (aq) ⇌ [CoCl4]2— (aq) + 6H2O (l)
The equilibrium constant, Kc, for this reaction is:

Kc = [[CoCl4]2—][6H2O]4
[[Co(H2O)6] ][Cl ]
2+ — 4
Kc = [[CoCl4]2—][6H2O]4
[[Co(H2O)6]2+][Cl—]4
[H2O(l)] is constant and therefore it is not included in the equation for
Kc.
Kstab = [[CoCl4] ]
2—
[[Co(H2O)6]2+][Cl—]4
Equilibrium constants like this for the formation of complex ions in
aqueous solution are called stability constants and the symbol Kstab is
sometimes used in place of Kc.
8.133 Stability constants
The stability constant is the equilibrium constant for the formation of the
complex ion in a solvent from its constituent ions or molecules.
Stability constants enable chemists to compare the stabilities of the

complex ions of a cation with different ligands.
The reaction to which Kstab relates always involves the displacement of

a solvent ligand, most frequently H2O.
The larger the stability constant, the more stable is the complex ion
compared with that containing water.
8.134 Stability constants
The values quoted usually give the stability of the complex relative to
the aqueous ion where the ligand is water.
The higher the value of the stability constant, the more stable the
complex.
Complex Kstab log Kstab

2− 5
[CuCl 4] 4.2 × 10 5.62
2+ 13
[Cu(NH3)4] 1.3 × 10 13.1
3− 31
[Fe(CN)6] 10 × 10 31
4− 24
[Fe(CN)6] 1.0 × 10 24
+ 7
[Ag(NH3)2] 1.7 × 10 7.23
solution are called stability constants and the symbol K stab is sometimes used
in 135
8. Stability
place of K c. constants
Stability constants enable chemists to compare the stabilities of the complex
The following table shows the stability constants of three complexes of
ions of a cation with different ligands. The larger the stability constant, the
the copper(ii) ion.
more stable is the complex ion compared with that containing water.
These show
Table 15.4 thatthe
shows thestability
relativeconstants
stabilities of thecomplexes
of three three copper(ii) complexes
of the copper(ii) ion.
These show that the relative stabilities of the three copper(ii) complexes are:
are:
[Cu(EDTA)]2− > [Cu(NH3)4(H2O)2 ]2+ > [CuCl4 ]2−
Ligand Complex ion K Tabl

Cl [CuCl4] 4.0 × 105 copp
NH3 [Cu(NH3)4(H2O)2]2+ 1.3 × 1013
EDTA [Cu(EDTA)] 6.3 × 1018
Complex ions and entropy

QUESTION
8.136 Skill Check
7 a Write expressions for the stability constants for the
following reactions:
i 2–
[PtCl4] (aq) + 2NH3(aq)
PtCl2(NH3)2(aq) + –
2Cl (aq)
ii 3+
[Cr(H2O)6] (aq) + –
2Cl (aq)
+
[Cr(H2O)4Cl2] (aq) + 2H2O(l)
iii 2+
[Ni(H2O)6] (aq) + 4NH3(aq)
2+
[Ni(NH3)4(H2O)2] (aq) + 4H2O(l)
b 3+
An iron(III) ion, Fe , in aqueous solution has six
8.137 Colour in complex ion
Transition metal have it’s outermost electrons in the d-orbitals. Some
along the axes, and others between the axes.
Ligands also have an electron cloud around them. When a ligand’s lone
pair forms a dative bond with the metal ion, there is bound to be
repulsion between the two electron clouds i.e. the electrons in the d
orbitals and the electron cloud around the ligands.
Colour, which is a characteristic property of transition metals, results
due to this repulsion between the electrons of the ligands and electrons
of the partially filled d-sublevel of the central metal ion.
This repulsion will vary between the two orbital systems as they are not
repelled equally by the electrons of the ligand. One orbital system will
be repelled more than the other, causing the electrons in the d sublevel
to become unstable and split into two different energy levels.
Each energy level contains only one type of orbital system i.e. either 2
orbital or 3 orbital, but never both. The orbitals that are repelled more
will be at a higher energy level and the one’s repelled less will be at a
lower energy level.
orbitals are split, with these two d orbitals at a slightly The exact energy diffe
higher energy level than the dyz, d xz and d xy orbitals degenerate d orbitals in a
Splitting
8.140 (Figure 24.14). of the d-orbital by many factors. One of
2+
A Cu ion has an electronic configuration of ligands that surround th
In a simple
[Ar] metal
9 ion,24.14
3d . Figure the shows
five 3d
howorbitals
the nine all have the
d electrons aresame have
energy
seen,and
a solution con
are saiddistributed between the non-degenerate
to be degenerate, orbitals formed
but in the presence of ligands, whereas a solution conta
the orbitals
divide into two energy levels and are now known as non degenerate
orbitals.
dx 2–y 2 dz 2
3d ∆E
energy absorbed
Cu2+(...3d9) from visible spectrum
degenerate that corresponds
3d orbitals to ∆E
dyz dxz dxy
splitting the
d orbitals to give
non-degenerate
orbitals
ctahedral shape and so they are closer to energy levels. In copper complexes, the rest of the visible
ctrons in the octahedral arrangement, spectrum that passes through the solution makes it appear
8.141 Splitting of the d-orbital
lsion between electrons. Therefore the
, with these two d orbitals at a slightly
blue in colour.
The exact energy difference (ΔE) between the non-
vel than the dyz, d xz and d xy orbitals degenerate d orbitals in a transition metal ion is affected
Both in degenerate and non by degenerate 3d of
many factors. One orbitals, theis the
these factors electrons
identity of are
the in
their ground
has an electronic state.
configuration of However, ligands
for a that
complex
surroundion to exhibit
the transition metalcolour,
ion. As you
24.14 shows how the nine d electrons are 2+
have seen, a solution containing Cu(H2O)6 is a light blue,
electrons must be excited
ween the non-degenerate orbitals formed
enough to transit from a lower energy2+
whereas a solution containing Cu(NH3)2(H2O)2 is a very
state
to a higher energy state by absorbing energy.
excited electron
absorbs energy
For this to happen the metal ∆E
dx –y
2 dz2 2
therefore has to have a partially filled

∆E
d orbital. energy absorbed
(...3d9) from visible spectrum
nerate that corresponds
rbitals to ∆E
dyz dxz dxy
splitting the the energy absorbed can be
d orbitals to give worked out by the equation:
non-degenerate
orbitals ∆E = hν
8.142 Splitting of the d-orbital
The energy gap created due to repulsion is very small and requires only
a small amount of energy for the electrons in the lower energy level to
be excited enough to jump to a higher energy level. This energy is
obtained from the visible light spectra.
The light spectra is not one energy but a series of colours having
different energies.
Electrons absorb energy in the form of some colours, while we see the
complimentary colours that were not absorbed.
8.143 Octahedral complex ion
The lone pair of ligands form the dative bonds of the complex ions. In
an octahedral complex, these bonds are along the x,y and z axes.
The electrons from these bonds start to repel the electrons of the d
orbitals of the metal ion.
The orbitals that were along the axes,dx —y

2 2 and dz are
2 repelled
more than the orbitals that were between the axes, dxy, dxz and dyz.
Therefore, the 2 orbital system moves to a higher energy level and the 3
orbital system moves to a lower energy level in the non-degenerate
orbitals
Energy level
(a) Five d orbitals in an (b) Five d orbitals in an (c) Five d orbitals in an

isolated gaseous ion ion in a uniform octahedral complex
– degenerate orbitals electric field – ion – non-degenerate
degenerate orbitals orbitals
Fig 25.22 The effect of ligands on the energy levels of the five 3d orbitals of the central metal cation
Without forming the complex ion, the d orbitals are degenerate and
don’t have any colour. But once they form a complex ion, the d orbital
becomes non degenerate.
This energy gap is small enough that electrons in the lower energy level
can move to a higher energy level by gaining energy from the visible
light spectra.
he the d orbitals split into two groups with
ransition different energies in an aqueous ion
tron
higher five d orbitals with the same
energy in a free gaseous ion
particular absorption of light at a
particular frequency can
promote an electron to a
2+
Cu (g) higher level
2+
Cu (aq)
Tip
ORANGE 600 BL
8.147 Theory of colour RED 650 GR
The colour seen is a solution of copper(II)sulphate is blue because

white light minus the red and yellow wavelengths are absorbed
colour being absorbed.
In case of Cu, it
absorbs the red-
Absorbance
orange frequency, and
we see the
complementary colour,
blue, that was not wavelength (nm)
300 400 500 600 700 800
absorbed. blue green yellow red
higher set. This means that the light coming out contains all the colours Fo
of the spectrum except orange and so appears blue, the complementary
8.148 Theory
colour to orange.
of colour col
lig
spe
Fo
ion
pre
sub
W
co
lig
3+ 4+
Let us consider the Sc ion or the Ti ion. These both have no
it except red and blue. The red and blue light passes t
8.149 Theory of colour
solution and appears purple (Figure 1).
R R
appears
G
purple
B B
absorbs
green
1 Solutions look coloured because they absorb some colours and

8.150 Theory of colour gradient
A colourless solution appears such because no colour is being
absorbed, and light passes through the solution. But when some light is
absorbed, the solution appears to be coloured.
The strength of the colour is determined by how much absorption of it’s

complimentary colour is occurring. The more the absorption, the
deeper the colour and vice versa.
8.151 Theory of colour gradient
Cu with H2O appears pale blue because it absorbs lesser red-orange
frequency compared to Cu with NH3(aq), which absorbs more of the red-
orange frequency and thus appears deep blue.
To absorb in the visible region, the substance must have two energy levels that
are very close together. Close energy levels come about in two ways, namely charge
8.152 Prediction of colour
transfer and d-to-d transitions.
urs observed when Example Absorption spectrum Colour Colour observed

n the visible region of absorbed (complementary)
absorption
green purple
KMnO4
blue yellow
K2CrO4
red blue
CuSO4.5H2O
400 700
wavelength/nm
8.153 Tetrahedral complex ion
In a tetrahedral the complex ions the bonds are not along the axes, but
rather, are found between the axes.Thus the dx2-y2 and dz2 are not
repelled as strongly as they were in an octahedral complex. And dxy,
dxz and dyz are repelled more strongly.
Therefore the dxy, dxz and dyz orbitals will move to a higher energy
level and dx2-y2 and dz2 will move to a lower energy level. And electrons
will transition from the 2 orbital system to the 3 orbital system.
8.154 Tetrahedral complex ion
For example in CuCl42- the bonds are not along the axes
2. 61 Tetrahedral Complex
8.155 Tetrahedral complex ion Ion
The degenerate orbitals therefore split into a higher 3 orbital and
The degenerate orbitals therefore split into a higher 3 orbital and lower 2 lowe
orbital
orbital degenerate
degenerate orbitals
orbitals once
once the the complex
complex ion is formed.
ion is formed.
dxy dxz dyz
⇅ ⇅
⇅ ⇅
Tetrahedral
CuCl42-
Complex
3d9 ⇅ ⇅
Cu2+ before complex dx2-y2 dz2
⇅ ⇅

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13.

1 First-row d-block elements – the transition elements

■ The d-block metals

These physical properties, together with fairly low chemical reactivity,

electrons and as you go across the 5

period, electrons are added to the 6

From potassium onwards, the orbitals of highest energy in the third

3p (max. : 6 electrons in 3 orbitals)

3s (max. : 2 electrons in 1 orbital)

However, once the 3d level is occupied by electrons, these repel the 4s

The 4s electrons are therefore pushed to a higher energy level, higher

Atom/ion Electron structure

Atom/ion Electron structure

(a) Complete the electron conﬁgurations for Ni and Ni .2+

number of unpaired electrons

(b) Solid potassium manganate(VII), KMnO4, decomposes on heating to form

The simple definition of transition metals as ‘d-block elements’ is

• Their compounds are usually white, unlike the compounds of

• They show little catalytic activity.

Scandium only forms Sc3+ (3d )

forms Zn (3d ) in all its compounds. They are therefore d-block

elements but not transition elements.

Therefore, electrons of an element with ions having completely empty

Figure 1 The d-block elements (shaded) and the transition metals

They show variable oxidation numbers in their compounds.

They form coloured ions in solution.

They can act as catalysts both as the elements and as their

They form complex ions.

The conductivities of the 3d-block metals are similar to those of

Hence, atomic radii decrease sharply from sodium to argon. At the

The increasing number of outer-shell electrons from sodium to argon

So while the nuclear charge is increasing across the period in the d-

This keeps the atomic radius, ionisation energy and electronegativity

This is caused by an increase in the nuclear charge without an increase

The effective nuclear charge increases considerably, and this causes a

The pattern is different across the d-block.

is a 4s-electron, and it is shielded by the inner 3d-electrons (as well as

1st ionisation energy/kJ mol–1 1800

This electron is subjected to a much stronger pull from the nucleus as it

Property Transition element Calcium

um Density Very high Lower than transition elements

ion, with ten electrons in the 3d sub-level.

The maximum stable oxidation state frequently corresponds to the

Oxidation states of transition metals

ds include the chloride ion,

Each of them varies in their electron arrangement in space. Four of

So, Cu2+(aq), Al3+(aq) and Ag+(aq) can be represented more accurately as

In excess ammonia solution, Cu2+ exists as [Cu(NH3)4(H2O)2]2+(aq) and

In addition to polar molecules, anions can also form co-ordinate bonds

Water is by far the most common ligand in complex ions.

Transition metal ions have a tendency to form complex ions because

CuSO4(anhydrous) [Cu(H2O)6]2+ (copper sulfate solution)

CHEMISTRY: FOR USE WITH T

A dative covalent bond (co-ordinate bond) is formed between each

The shape of the complex ion depends on the number of ligands

These geometrical shapes are the same as those assumed by

According to VSEPR theory, the coordinate bonds take on the

8.66 Octahedral complex - [Cr(NH ) ]

nsition elements and qualitative analysis