FIRST ROW

TRANSITION
ELEMENTS
 Complex ions
A complex ion is a central metal ion bonded to a number of
molecules or anions called ligands. When the metal is a transition
element, its ion is called a transition metal ion. The ligands have a
lone electron pair it donates to the transition metal ion forming a
dative covalent bond. Some examples of ligands include
H2 O, NH3 , Cl− and CN −
 Note: Dative covalent bonds are formed because the d electrons in
transition elements do not shield the outer electrons well from nuclear
charge, so the poorly shielded nucleus attract lone pairs of electrons to form
co-ordinate bonds
The number of dative covalent bonds formed between the central ion and
the ligand is called the co-ordination number. The most common co-
ordination numbers are six and four, but two is not uncommon.

Read pg. 247 in textbook for more info

 An example of a complex is
[Cu(NH3 )4 H2 O)2 2+ .

Cu2+ ion has a co-ordination

number of six . This is because in
the picture shown, there are six
bonds connecting the ligands to Another example is CuCl4 2−
.
the central ion. This has a co-ordination number
of four.
 Types of ligands.
Ligands may be classified according to the number of bonds they
can form with central metal ion. This classification is known as the
denticity of the ligand.
Note that the number of bonds formed is not equal to the number
of lone pairs on the ligand. Each co-ordinating atom only donates
one lone pair to the central ion.
 Some types of ligands include:
1. Monodentate ligands: They form one bond per ligand e.g.,
H2 O, NH3 , Cl− and CN −
2. Bidentate ligands: They form two bonds per ligand e.g.,
NH2 − CH2 − CH2 − NH2 (1,2-diaminoethane).
3. Polydentate ligands: They form many bonds per ligands e.g.,
EDTA (ethylenediaminetetraacetate ion).
 SHAPES OF COMPLEX IONS
The shape of a complex ion depends on the number of ligands bonded to
the central ion.
Complexes with co-ordination number 2 give a linear shape with bond angle
of 180°
Most complexes with co-ordination number 4 tend to be tetrahedral with
bond angle of 109.5°. A few show square planar shape with bond angle of
90°
Complexes with co-ordination number 6 give an octahedral shape with bond
angle of 90°
 Chelates are ring complexes formed when bidentate or
polydentate ligands binds to the metal ion. These complexes
have enhanced stability as the central ion is held firmly by the
ligands. Examples of chelates are [Ni(en)3 ]2+ and [Cr(en)3 ]3+ .
They contains three bidentate ligands coordinated around the
respective central metal ion in an octahedral manner.

Read pg. 249 & 250.

Naming complex
ions
The name of a complex ion has
four parts.
1. The first part addresses the
number of ligands bonded to
the central ion.
 2. The second part names the type of ligand present. If a
complex ion contains more than one ligand, the names are
written in alphabetical order.
 3. The third part names the
metal. If the metal is positively
charge, the English name is
used. If the metal is negatively
charged, the Latin name with
suffix −𝑎𝑡𝑒 is used.
4. The last part gives the oxidation state of the central metal ion.
This is written in roman numerals enclosed in brackets e.g. (III)
Examples of naming of complexes include:
[Cu H2 O)6 2+ is hexaaquacopper (II) ion. Hexa means 6, aqua
means water, the metal which is copper has an oxidation state
of +2 (II)
[𝑁𝑖𝐶𝑙4 ]2− is tetrachloronickelate (II) ion. There are 4 (tetra)
chlorines (chloro) around nickel in an overall negative ion
(nickelate) which has an oxidation number of +2.
More examples to be seen in textbook. Pg.251 ☺
 Ligand exchange reactions
A ligand exchange reaction is one in which one ligand in a
complex ion is replaced by another ligand. This reaction occurs
since some ligands form stronger bonds with a particular metal
ion than other ligands. Thus, stronger ligands may displace
weaker ligands.
 Usually, it is water molecules (H2 O) that is being replaced.
An example of this reaction is when cyanide ions 𝐶𝑁 − are
added to aqueous Fe (III) ions [Fe(H2 O)6 ]3+ . The aqua ligands
are replaced by the cyanide ligands.
[Fe(H2 O)6 ]3+ (aq) + 6CN − (aq) ↔ [Fe(CN)6 ]3− (aq) +6H2 O(𝑙)
 An example of this reaction is when aqueous ammonia is
added to hexaaquacopper (II) ions.
When a few drops of NH3 is added, it accepts protons from two
aqua ligands attached to the Cu2+ ions to form copper (II)
hydroxide, a pale blue precipitate.
[𝐂𝐮(𝐇𝟐 𝐎)𝟔 ]𝟐+ (𝒂𝒒) + 𝟐𝐍𝐇𝟑 (𝒂𝒒) ↔ [𝐂𝐮 (𝐎𝐇)𝟐 (𝐇𝟐 𝐎)𝟒 ](s)+ 𝟐𝐍𝐇𝟒 + (𝒂𝒒)
 When excess ammonia is added, the precipitate dissolves and the
ammonia replaces two of the water ligands and the hydroxide ligands
to give a deep blue solution called tetraamminediaquacopper (II) ions
[𝐂𝐮(𝐎𝐇)𝟐 (𝐇𝟐 𝐎)𝟒 ](s)+ 𝟒𝐍𝐇𝟑 (𝒂𝒒) ↔ [𝐂𝐮(𝐍𝐇𝟑 )𝟒 (𝐇𝟐 𝐎)𝟐 ]𝟐+ 𝐚𝐪 + 4𝐇𝟐 𝐎 (𝐥)

The overall reaction can be shown by an equilibrium equation:

[𝐂𝐮(𝐇𝟐 𝐎)𝟔 ]𝟐+ (𝒂𝒒) + 𝟒𝐍𝐇𝟑 (𝒂𝒒) ↔ [𝐂𝐮(𝐍𝐇𝟑 )𝟒 (𝐇𝟐 𝐎)𝟐 ]𝟐+ 𝐚𝐪 + 4𝐇𝟐 𝐎 (𝐥)
Like any other equilibrium reaction, this one has an associated
equilibrium constant called stability constant, 𝐾𝑠𝑡𝑎𝑏 .

[[𝐂𝐮(𝐍𝐇𝟑 )𝟒 (𝐇𝟐 𝐎)𝟐 ]𝟐+ ]

𝐾𝑠𝑡𝑎𝑏 =
[[𝐂𝐮 𝐇𝟐 𝐎)𝟔 ]𝟐+ [𝐍𝐇𝟑 ]𝟒
pg 252.
 Haemoglobin
Haemoglobin is an iron-containing protein found in red blood cells that
transport oxygen from the lungs to the rest of the body. It consists of
four globular proteins. At the centre of each protein is an Fe2+ ion
complex known as haem. The haem group consists of the Fe2+ ion held
in a heterocyclic ring called porphyrin. The central Fe2+ ion has a
coordination number of 6 and is bound to four nitrogen atoms of the
porphyrin in one plane, a nitrogen from the globular protein, and either
water or molecular oxygen.
In the lungs, oxygen binds to Fe2+ ion forming oxyhaemoglobin.
In other parts of the body, the bound oxygen is replaced by an
aqua ligand forming deoxyhaemoglobin. This allows
haemoglobin to transport oxygen from the lungs to the rest of
the body. Haemoglobin can transport 4 oxygen molecules at a
time due to the four globular proteins present.
See textbook for more diagrams. Pg. 254&255
Stronger ligands such as carbon monoxide and cyanide can
compete with and replace oxygen at the bonding site. This
reaction is irreversible and prevents haemoglobin from
transporting oxygen. Haemoglobin bonds with carbon
monoxide forming a very bright red form of haemoglobin
called carboxyhaemoglobin and this accounts for the
poisonous nature of these substances.