Transition Elements & Cordination Chemistry (NCUK)

NCUK -Chemistry Department Page:1
Topic H- Transition Metals and Coordination Chemistry

THE TRANSITION ELEMENTS (d-BLOCK)
SLOs H1, H2
d-Block Elements (Transition metals):
Originally the name transition metals was derived from the fact that their chemical properties
were transitional between those of s and p-block elements.
Now according to IUPAC, transition metals are defined as metals which have incomplete d -
subshell either in neutral atom or in their ions.
The transition metals, d-block elements are arranged from groups 3-12, i.e., in between s and
p block elements, and defined by their incomplete d-electron configuration. In the d orbital,
their valence electrons have been put.
OR
“d-block elements” are defined as elements in which the last differentiating electron enters
the d-orbitals of the penultimate shell, i.e. (n–1) d where n is the last shell.
They are primarily classified into three groups. The d-orbitals of the penultimate energy level
of atoms received electrons, giving rise to four rows of the transition metals, i.e., 3d, 4d, 5d,
and 6d.
1. First transition series (Sc to Cu)
2. Second transition series (Y to Ag)
3. Third transition series (La and the elements from Hf to Au)
The f-block consists of elements in which 4 f and 5 f orbitals are progressively filled.
Lanthanides and actinides are f-block elements found in the sixth and seventh series. They
are placed in a separate panel at the bottom of the periodic table. Lanthanides are the
fourteen elements ranging from Cerium to Lutetium. Actinides, on the other hand, are the
fourteen elements ranging from nuclear number 90 (Thorium) to 103 (Lawrencium).
The names transition metals and inner transition metals are often used to refer to the
elements of d-and f-blocks respectively.
metals,
Definition of the Transition Metals:

Now, according to IUPAC, transition metals are defined as metals that have an incomplete d
subshell, either in the neutral atom or in their ions. Because zinc, cadmium, and mercury in
group 12 have full d10 configuration in both their ground and common oxidation states,
they are not considered transition metals. However, being the end members of the 3d, 4d,
and 5d transition series, respectively, their chemistry is studied along with the chemistry of the
transition metals.
The presence of partially filled d or f orbitals in their atoms makes transition elements
different from those of the non-transition elements. Hence, transition elements and their
compounds are studied separately. However, the usual theory of valence as applicable to the
non-transition elements can be successfully applied to the transition elements as well.
Various precious metals such as silver, gold, and platinum and industrially important metals
like iron, copper, and titanium belong to the transition metals series.
Kings International School Yangon, Myanmar

Transition metals are classified into two types: transition metals and inner transition
metals. Electron configurations are used to categorise them.
All these transition elements are shown below in the table.
1St Transition Series ( 3d1– 104s1–2) : Los H1

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z 21 22 23 24 25 26 27 28 29 30
4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 3 5 5 6 7 8 10 10
NOTE:
The electronic configurations of the outer orbitals of Zn, Cd, Hg, and Cn are represented by the
general formula (n-1)d10ns2. The orbitals in these elements are completely filled in the ground
state as well as in their common oxidation states. Therefore, they are not regarded as
transition elements or d -block elements.
However, being the end members of the 3d, 4d and 5d transition series, respectively, their
chemistry is studied along with the chemistry of the transition metals.
General Electronic Configuration of d-Block Elements

In general, the electronic configuration of outer orbitals of these elements
is (n-1)d1– 10ns1–2except for Pd where its electronic configuration is 4d105s0.
The (n–1) stands for the inner d orbitals which may have one to ten electrons and the
outermost ns orbital may have one or two electrons.
• However, this generalisation has several exceptions because of very little energy
difference between (n-1)d and ns orbitals. Furthermore, half and completely filled sets
of orbitals are relatively more stable. A consequence of this factor is reflected in the
electronic configurations of Cr and Cu in the 3d series. For example, consider the case of
Cr, which has 3d5 4s1 configuration instead of 3d44s2; the energy gap between the two
sets (3d and 4s) of orbitals is small enough to prevent electron entering the 3d orbitals.
Similarly in case of Cu, the configuration is 3d104s1 and not 3d94s2.
• The d orbitals of the transition elements bulge out to the periphery of an atom more
than the other orbitals (i.e., s and p), hence, they are more influenced by the
surroundings as well as affect the atoms or molecule surrounding them. In some
respects, ions of a given dn configuration (n = 1 – 9) have similar magnetic and electronic
properties. With partly filled d orbitals these elements exhibit certain characteristic
properties such as display of a variety of oxidation states, formation of coloured
ions and entering into complex formation with a variety of ligands.
• The transition metals and their compounds also exhibit catalytic property and
paramagnetic behaviour.
There are greater similarities in the properties of the transition elements of a horizontal row in
contrast to the non-transition elements. However, some group similarities also exist. We shall

first study the general characteristics and their trends in the horizontal rows (particularly 3d
row) and then consider some group similarities.
Properties of Transition Metals

With partly filled d orbitals these elements exhibit certain characteristic properties such as
• display of a variety of oxidation states,
• they form coloured ions
• they form complexes with a variety of ligands.
• The transition metals and their compounds also exhibit catalytic property
• They show paramagnetic behaviour.
Physical Properties
Nearly all the transition elements display typical metallic properties such as high tensile
strength, ductility, malleability, high thermal and electrical conductivity, and metallic luster.
With the exceptions of Zn, Cd, Hg, and Mn, they have one or more typical metallic structures
at normal temperatures.
1) Melting point & boiling point The transition metals (with the exception of Zn, Cd and Hg)
are very hard and have low volatility. Their melting and boiling points are high.
2) Variation in Atomic and Ionic Sizes of Transition Metals In general, ions of the same
charge in a given series show progressive decrease in radius with increasing atomic number.
This is because the new electron enters a d orbital each time the nuclear charge increases
by unity.
It may be recalled that the shielding effect of a d electron is not that effective, hence the net
electrostatic attraction between the nuclear charge and the outermost electron increases
and the ionic radius decreases.
3) Ionisation enthalpy There is an increase in ionisation enthalpy along each series of the
transition elements from left to right due to an increase in nuclear charge which
accompanies the filling of the inner d orbitals.
Chemical Properties (SOLs H9)
Some of the chemical properties of the transition metals are listed below:
1) Transition metals can have variable oxidation states.

2) They also form complex ions.
3) They produce coloured compounds and ions.
4) In addition, they have good catalytic properties.
5) Finally, transition metals don’t react much with water or oxygen
The first four chemical properties in the list above (variable oxidation states, complex ion
formation, coloured ions, and catalytic activity) make transition metals quite interesting.
Although these particular properties aren’t unique to transition metals, they do make them
stand out from the other elements! All four characteristic properties can be explained by
the incomplete d-subshell found in transition metals. Let’s look at them in more detail.

With partially filled d orbitals, which bulge out to the periphery of an atom more than the
other orbitals (i.e., s and p), they are more influenced by the surroundings. Hence, these
transition elements exhibit certain characteristic properties, such as the display of a variety of
oxidation states, the formation of coloured compounds and ions, and entering into complex
formation with a variety of ligands, etc.
1) Variable oxidation states

The elements which give the greatest number of oxidation states
occur in or near the middle of the series.
1St Transition Series (Oxidation States)

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3
+3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
▪ Manganese, for example, exhibits all the oxidation states from +2 to +7.
▪ The lesser number of oxidation states at the extreme ends stems from either too few
electrons to lose or share (Sc, Ti), or too many d electrons (hence fewer orbitals available
in which to share electrons with others) for higher valence (Cu, Zn).
Thus, early in the series, scandium(II) is virtually unknown, and titanium (IV) is more
stable than Ti(III) or Ti(II).
At the other end, the only oxidation state of zinc is +2 (no d electrons are involved).
The maximum oxidation states of reasonable stability correspond in value to the sum of
the s and d electrons up to manganese (TiIVO2, VVO2+,CrV1O42–, MnVIIO4–) followed by a
rather abrupt decrease in stability of higher oxidation states, so that the typical species to
follow are FeII,III, CoII,III, NiII, CuI,II, ZnII.
The variability of oxidation states, a characteristic of transition elements, arises out of
incomplete filling of d orbitals in such a way that their oxidation states differ from each
other by unity, e.g., VII, VIII, VIV, VV. This is in contrast with the variability of oxidation
states of non- transition elements, where oxidation states normally differ by a unit of
two.
2) Formation of complex compounds

Transition metal ions form a large number of complex compounds.
The transition metals form a large number of complex compounds. This is due to the
comparatively smaller sizes of the metal ions, their high ionic charges and the
availability of d orbitals for bond formation.
Complex compounds are those which have a metal ion at their centre with a number of
other molecules or ions (negative ions or anions) surrounding it. These are lined up with a
number of negative ions (anions) or neutral molecules having a lone pair of electrons. These
molecules or ions are attached to the central ion by coordinate bonds (dative bonds). In
some cases, bonding is more complicated.

These compounds are also called coordination complexes.

These negative ions or neutral molecules are called ligands. They donate lone pairs of
electrons to the central transition metal ion, forming co-ordinate bonds, also called dative
covalent bonds. Ligands molecules or ions surrounding the central metal ion.
Few examples of complexes (complex ions) are:
[Cu(NH3)4]2+ , [Cr(NH3)6]3+, [Fe(CN)6]3¯ , [Fe(CN)6]4¯ , [Zn (NH3)4]2+ , [Ni (CN)4]2¯,
[Ni (CO)4].
• The complex ion carrying a positive charge is called cationic complex, the one with
negative charge is called anionic complex and with no charge is called a neutral complex.
Such compounds are not formed by ‘s’ and ‘p’ block elements.
The transition elements form complexes because of following reasons:―
(i) Small size and high charge density of the ions of transition metals.
(ii) Presence of vacant d-orbitals of appropriate energy which can accept lone pairs of
electrons donated by other groups (ligands).
Alfred Werner (1866-1919), a Swiss chemist was the first to formulate his ideas about the
structures of coordination compounds. He prepared and characterised a large number of
coordination compounds and studied their physical and chemical behaviour by simple
experimental techniques. Werner proposed the concept of a primary valence and
a secondary valence for a metal ion. Binary compounds such as CrCl3, CoCl2 or PdCl2 have
primary valence of 3, 2 and 2 respectively.
In a series of compounds of cobalt(III) chloride with ammonia, it was found that some of the
chloride ions could be precipitated as AgCl on adding excess silver nitrate solution in cold
but some remained in solution.
1 mol CoCl3.6NH3 (Yellow) gave 3 mol AgCl
1 mol CoCl3.5NH3 (Purple) gave 2 mol AgCl
1 mol CoCl3.4NH3 (Green) gave 1 mol AgCl
1 mol CoCl3.4NH3 (Violet) gave 1 mol AgCl
These observations, together with the results of conductivity measurements in solution can
be explained if
(i) six groups in all, either chloride ions or ammonia molecules or both, remain bonded to
the cobalt ion during the reaction and
(ii) the compounds are formulated, where the atoms within the square brackets form a
single entity which does not dissociate under the reaction conditions. Werner proposed
the term secondary valence for the number of groups bound directly to the metal ion; in
each of these examples the secondary valences are six.
Colour Formula Solution Conductivity

Corresponds to
Yellow [Co(NH3)6]3+3Cl– 1:3 electrolyte
Purple [CoCl(NH3)5]2+2Cl– 1:2 electrolyte
Green [CoCl2(NH3)4]+Cl– 1: 1 electrolyte
Violet [CoCl2(NH3)4]+Cl– !: 1 electrolyte

Note that the last two compounds in above Table have identical empirical
formula, CoCl3.4NH3, but distinct properties. Such compounds are termed as isomers.
Werner in 1898, propounded his theory of coordination compounds.

The main postulates are:
1. In coordination compounds metals show two types of linkages (valences)-primary and
secondary.
2. The primary valences are normally ionisable and are satisfied by negative ions.
3. The secondary valences are non ionisable. These are satisfied by neutral molecules or
negative ions. The secondary valence is equal to the coordination number and is fixed
for a metal.
4. The ions/groups bound by the secondary linkages to the metal have characteristic spatial
arrangements corresponding to different coordination numbers.
In modern formulations, such spatial arrangements are called coordination polyhedra.
The species within the square bracket are coordination entities or complexes and the ions
outside the square bracket are called counter ions.
He further postulated that octahedral, tetrahedral and square planar geometrical shapes
are more common in coordination compounds of transition metals. Thus, [Co(NH3)6]3+,
[CoCl(NH3)5]2+ and [CoCl2(NH3)4]+ are octahedral entities, while [Ni(CO)4] and [PtCl4]2– are
tetrahedral and square planar, respectively.
The coordination number (CN) of a metal ion in a complex can be defined as the number of
ligand donor atoms to which the metal is directly bonded.
On the basis of the following observations made with aqueous solutions, assign secondary
valences to metals in the following compounds:
Exchange of ligands result in change in coordination number (SLOs H8)
Moles of AgCl precipitated

Formula Per mole of the compound with
Excess AgNO3
(i) PdCl2.4NH3 [PdCl(NH3)4]3+2Cl– 2 mole
(ii) NiCl2.6H2O [Ni(NH3)6]2+2Cl– 2 mole
(iii) PtCl4.2HCl [PtCl4(HCl)2] 0 mole
(iv) CoCl3.4NH3 [CoCl2(NH3)4]+Cl– 1 mole
(v) PtCl2.2NH3 [PtCl2(NH3)2] 0 mole
(i) Secondary 4 (ii) Secondary 6 (iii) Secondary 6 (iv) Secondary 6 (v) Secondary 4
What are the coordination compounds? (SLOsH3)
The addition compounds that retain their identity in the solid and dissolved states are
known as coordination compounds.
The addition compounds fall into two categories, namely, double salts and coordination
compounds. The double salts are stable in their solid states but break up into their

constituents in their dissolved states. In such compounds, the individual properties of the
constituents are not lost.
Double Salts
The double salts such as KCl.MgCl2.6H2O, Mohr’s salt, FeSO4.(NH4)2SO4.6H2O, potash alum,
KAl(SO4)2.12H2O, etc. dissociate into simple ions completely when dissolved in water.
for example, the crystalline substance called Mohr’s salt [FeSO4 ▪ (NH4)2SO4▪6H2O]
which is formed by combining together (NH4)2SO4, FeSO4 and H2O in stoichiometric
proportions as shown below.
(NH4)2SO4 + FeSO4 +6 H2O → FeSO4 ▪ (NH4)2SO4▪6H2O
An aqueous solution of Mohr’s salt shows the properties of Fe2+, SO42¯ and NH4+ ions
Coordination compounds /Complex ions
In coordination compounds, the individual properties of the constituents are usually lost.
For example, when we mix an aqueous solution of CuSO4 with an aqueous solution of
ammonia, a deep blue-colored solution is obtained. The blue-colored solution does not
show the presence of Cu2+ ions, but instead it contains cupro-ammonium ions [Cu
(NH3)4]2+, which are formed by the combination of Cu2+ ions and four ammonia molecules.
Such ions are known as complex ions. Similarly, by mixing definite proportions of aqueous
solutions of KCN and Fe(CN)2 that do not dissociate into Fe2+ and CN- ions, a complex ion
[Fe(CN)4]4- of K4[Fe(CN)4] is formed.
The salts of complex ions are called complex compounds or coordination compounds.
In the formation of a coordinate bond, the anions or neutral molecules act as the electron
pair donors, whereas the central metal ion acts as the electron pair acceptor.
Double salt coordination compounds
• The double salts are stable in the solid • The coordination compounds are stable
states. in the solid states.
• They break up into its constituents in • They don’t break up into its
dissolved state. constituents in dissolved state.
• The individual properties of the • in coordination compounds the individual
constituents are not lost in dissolved state properties of the constituents are usually
For example, the crystalline substance lost.
called Mohr’s salt [FeSO4 ▪ (NH4)2SO4▪6H2O] • For example, when we mix aqueous
shows the properties of shows the solution of CuSO4 with aqueous solution
properties of Fe2+, SO42¯ and NH4+ ions in of ammonia, a deep blue colour solution
aqueous solution is obtained. The blue coloured solution
does not show the presence of Cu2+ ions
but instead it contains cupro-ammonium
ions; [Cu (NH3)4]2+ which are formed by
the combination of Cu2+ ions and four
ammonia molecules.

Some important terms pertaining to Coordination compounds

a ) Coordination entity 
A coordination entity consists of a central metal atom or ion bonded to a fixed number of
ions or molecules. For example, [CoCl3(NH3)3] is a coordination entity in which the cobalt
ion is surrounded by three ammonia molecules and three chloride ions.
Other examples are [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+.
b ) Central atom/ion 
In a coordination entity, the atom/ion to which a fixed number of ions/groups are bound
in a definite geometrical arrangement around it, is called the central atom or ion. For
example, the central atom/ion in the coordination entities: [NiCl2(H2O)4], [CoCl(NH3)5]2+
and [Fe(CN)6]3– are Ni2+, Co3+ and Fe3+, respectively.
These central atoms/ions are also referred to as Lewis acids.
c ) Ligands 
The ions or molecules bound to the central atom/ion in the coordination entity are called
ligands. These may be simple ions such as Cl–, small molecules such as H2O or NH3, larger
molecules such as H2NCH2CH2NH2 or N(CH2CH2NH2)3, or even macromolecules, such as
proteins.
Nature or Ligands:
Simple ligands include water, ammonia, and chloride ions.
What all these have got in common is active lone pairs of electrons in the outer energy
level. These are used to form co-ordinate bonds with the metal ion.

NOTE:
All ligands are lone pair donors. In other words, all ligands function as Lewis bases.
Unidentate Ligands
When a ligand is bound to a metal ion through a single donor

atom, as with Cl–, H2O or NH3, the ligand is said to be
unidentate.
Types of Ligands When a ligand can bind through two donor atoms as in
H2NCH2CH2NH2 (ethane-1,2-diamine) or C2O42– (oxalate),
the ligand is said to be didentate.
Polydentate Ligands
When a when several donor atoms are

present in a single ligand as in N(CH2CH2NH2)3, the ligand
is said to be polydentate. Ethylenediaminetetraacetate ion
(EDTA4–) the ligand is said to be polydentate.
1. Unidentate (one donor site) or Monodentate

[Uni = one + dent = tooth] i.e. one point of attachment
Example: NH3, CN¯, Cl¯, Br¯, I¯, :OH¯, NO2¯
2. Ambidentate Ligand
Ligand which has two different donor atoms and either of the two ligetes in the complex is
called ambidentate ligand.
NO2– and SCN– ions are the examples of such ligands. NO2– ion can coordinate either through
nitrogen or through oxygen to a central metal atom/ion.
Similarly, SCN– ion can coordinate through the sulphur or nitrogen atom.
NO2–
¯ ¯
SCN–

3. Polydentate Ligand
Ethylenediaminetetraacetate ion (EDTA4–) is an important hexadentate ligand. It can bind
through two nitrogen and four oxygen atoms to a central metal ion.
EDTA4-
Chelating Ligand
When a di- or polydentate ligand uses its two or more donor atoms simultaneously to bind a single
metal ion, it is said to be a chelate ligand. The number of such ligating groups is called the
denticity of the ligand. Such complexes, called chelate complexes tend to be more stable than
similar complexes containing unidentate ligands (Greek word chelate means claw).
The complex formed by Cu (II) and Pt (II) ions with ethylenediamine are metal chelates represented
as follows:
Ligand Charge Donor atom Type Name given in the

complex
Monodentate
NH3 0 N ammine
(Neutral)
Monodentate
H2O 0 O Aqua or aquo
(Neutral)
Monodentate
Cl¯, Br¯, I= X¯ –1 X Halo
(Negative)
Monodentate
:OH¯ –1 O hydroxo
(Negative)
COO¯ Two oxygen

Bidentate
| –2 (O¯ ) atoms oxaloto
(Negative)
COO¯
NH2 One nitrogen Bidentate

CH2 –1 and (Both
glycinato
COO¯ one O¯ atom Neutral &
Negative)

d) Coordination number  (SLOsH2, SLOs 8)

The coordination number (CN) of a metal ion in a complex can be defined as the number of
ligand donor atoms to which the metal is directly bonded. For example, in the complex ions,
[PtCl6]2 and [Ni(NH3)4]2+, the coordination number of Pt and Ni are 6 and 4 respectively.
Similarly, in the complex ions, [Fe(C2O4)3]3– and [Co(en)3]3+, the coordination number of both
Fe and Co, is 6 because C2O42– and en (ethane-1,2-diamine) are didentate ligands.
[Fe(C2O4)3]3- [Co(en)3]3+
It is important to note that the coordination number of the central atom/ion is determined
only by the number of sigma bonds formed by the ligand with the central atom/ion. Pi bonds,
if formed between the ligand and the central atom/ion, are not counted for this purpose.
(e) Coordination sphere 

The central atom/ion and the ligands attached to it are enclosed in square brackets and are
collectively termed as the coordination sphere. The ionisable groups are written outside the
bracket and are called counter ions. For example, in the complex K4[Fe(CN)6], the coordination
sphere is [Fe(CN)6]4– and the counter ion is K+.
(f) Coordination polyhedron 

The spatial arrangement of the ligand atoms that are directly attached to the central atom/ion
defines a coordination polyhedron about the central atom. The most common coordination
polyhedra are octahedral, square planar and tetrahedral. For example, [Co(NH3)6]3+ is
octahedral, [Ni(CO)4] is tetrahedral, and [PtCl4]2– is square planar.

The following figure shows the shapes of different coordination polyhedral.
Bond Angle Bond Angle Bond Angle Bond Angle Bond Angle
900 109.5 0 900 900 & 1200 900
900
(g) Oxidation number of central atom 

The oxidation number of the central atom in a complex is defined as the charge it would carry
if all the ligands are removed along with the electron pairs that are shared with the central
atom. The oxidation number is represented by a Roman numeral in parenthesis.
following the name of the coordination entity.
For example, oxidation number of copper in [Cu(CN)4]3– is +1 and it is written as Cu(I).
(h) Homoleptic and heteroleptic complexes

Complexes in which a metal is bound to only one kind of donor groups, e.g., [Co(NH3)6]3+, are
known as homoleptic. Complexes in which a metal is bound to more than one kind of donor
groups, e.g., [Co(NH3)4Cl2]+, are known as heteroleptic.
Shape of complexes (SLOs H5)

In the case of transition metals, the most common coordination number is 6. But
examples of 4 and 2 are not uncommon.
In complexes with coordination number 6, the ligands usually occupy octahedral

positions. While complexes with a coordination number of 4 usually have a tetrahedral
arrangement of ligands, a few complexes with a coordination number of 4 have a
square planar geometry. Complexes with coordination number 2 usually have a linear
arrangement of ligands.
(i) Shape of the complexes with coordination number two:

Complexes with coordination number two usually have a linear arrangement of
ligands. For example diammine silver (I) ion.
[ H3N Ag NH3]+
(ii) Shape of the complexes with coordination number four:
Complexes with a coordination number of four usually have a tetrahedral
arrangement of ligands. But a few complexes with a coordination number of 4 have
square planar geometry.

2+
NH3
Cl NH3
Pt 2+
Zn
Cl NH3
NH3 NH3
NH3
Tetrahedral Square planar
NH3 2+
NH3
900
Cu
NH3 NH3
Square planar
(iii) Shape of the complexes with coordination number six:

In complexes with coordination number six, the ligands usually occupy octahedral
positions.
Cl
NH3 NH3
Co
M NH3 NH3
Cl
Octahedral
NOTE:
Use wedges (solid lines) to show the bonds on the plane of the paper, and use a
dashed line to show the bonds away from the viewer.
Bonding in Coordination Compounds 
Werner was the first to describe the bonding features in coordination compounds. But
his theory could not answer basic questions like:
(i) Why only certain elements possess the remarkable property forming coordination
compounds?
(ii) Why the bonds in coordination compounds have directional properties?
(iii) Why coordination compounds have characteristic magnetic and optical properties?
Many approaches have been put forth to explain the nature of bonding in coordination
compounds viz. Valence Bond Theory (VBT), Crystal Field Theory (CFT), Ligand Field
Theory (LFT) and Molecular Orbital Theory (MOT). We shall focus our attention on
elementary treatment of the application of VBT and CFT to coordination compounds.
Limitations of Valence Bond Theory 
While the VB theory, to a larger extent, explains the formation, structures and magnetic
behaviour of coordination compounds, it suffers from the following shortcomings:
(i) It involves a number of assumptions.

(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the colour exhibited by coordination compounds.
(iv) It does not give a quantitative interpretation of the thermodynamic
or kinetic stabilities of coordination compounds.
(v) It does not make exact predictions regarding the tetrahedral and square planar
structures of 4-coordinate complexes.
(vi) It does not distinguish between weak and strong ligands
Crystal field splitting:

Most of the transition metal compounds (ionic as well as covalent) are coloured both in
solid state and in aqueous solution, in contrast to the compounds of the s and p-block
elements.
Reason:
The presence of an incomplete d-subshell causes the colour of a transition metal
compound. Further, when an anion approaches the transition metal ions, their d-

orbitals do not remain degenerate (i.e., do not remain of the same energy). They split
into two sets, one with lower energy and the other with higher energy. This is called
crystal field splitting.
Thus, the electron can jump from lower energy d-orbitals to higher energy d-orbitals.
The required amount of energy to do this is obtained by the absorption of light of a
particular wavelength in the region of visible light. One or more electrons from a lower
higher level within the same d-sub shell are promoted.
Since the different d-orbitals belonging to the same sub-shell have slightly different
energies, the energy required to promote such an electron is very small. Radiations of
light corresponding to such a small amount of energy are available within the visible
region of light. The transition metal ions have the property to absorb such radiation
from visible light and appear coloured due to the emission of the remainder as
coloured light. If a substance absorbs the wavelength corresponding to red light,
transmitted light will consist of wavelengths corresponding to the other colors,
especially greenish blue.
The crystal field theory (CFT) is an electrostatic model that considers the metal-ligand
bond to be ionic, arising purely from electrostatic interactions between the metal ion
and the ligand. Ligands are treated as point charges in the case of anions or point
dipoles in the case of neutral molecules.
The five d orbitals in an isolated gaseous metal atom or ion have the same energy, i.e.,
they are degenerate. This degeneracy is maintained if a spherically symmetrical field of
negative charges surrounds the metal atom or ion. However, when this negative field is
due to ligands (either anions or the negative ends of dipolar molecules like NH3 and H2O)
in a complex, it becomes asymmetrical and the degeneracy of the d orbitals is lifted. It
results in the splitting of the d orbitals. The pattern of splitting depends on the nature
of the crystal field.
Degenerate orbitals: Orbitals having same energy
The important point of CFT:

1. This theory considered the metal-ligand bond is purely ionic
2. The electrostatic interaction between metal ion and ligands
3. The ligand is anion metal atom is a cation
4. If the ligand is a neutral molecule the negative ends of the dipole is attractive
towards the metal atom
5. It treats the ligand is a point of negative charge
6. The arrangement of ligand around the central metal ion in such a way that repulsion
should be minimum
❖ It will decrease the force if there will be more force of attraction. it means there is low
energy.
❖ It will increase the force if there will be more force of attraction. it means there is high
energy.
(a) Crystal field splitting in octahedral coordination entities

In an octahedral coordination entity with six ligands surrounding the metal atom/ion,
there will be repulsion between the electrons in metal d orbitals and the electrons (or
negative charges) of the ligands.
Such a repulsion is more when the metal d orbital is directed towards the ligand than
when it is away from the ligand. Thus, the 𝑑𝑥 2−𝑦2 and 𝑑𝑧 2 orbitals which point
towards the axes along the direction of the ligand will experience more repulsion and
will be raised in energy; and the dxy, dyz and dxz orbitals which are directed between
the axes will be lowered in energy relative to the average energy in the spherical
crystal field. Thus, the degeneracy of the d orbitals has been removed due to ligand
electron-metal electron repulsions in the octahedral complex to yield three orbitals of
lower energy, 𝑡2𝑔 set and two orbitals of higher energy, 𝑒𝑔 set.
This splitting of the degenerate levels due to the presence of ligands in a definite
geometry is termed as crystal field splitting and the energy separation is denoted by
∆o (the subscript o is for octahedral). Thus, the energy of the two 𝑒𝑔 orbitals will
increase by (3/5) ∆o and that of the three t2g will decrease by (2/5) ∆o. The crystal field
splitting, ∆o, depends upon the field produced by the ligand and charge on the metal
ion. Some ligands are able to produce
strong fields in which case, the splitting will be large whereas others produce weak
fields and consequently, result in small splitting of d orbitals.
• ∆0 = Crystal field Splitting energy

• Magnitude of ∆0 is depends upon types of ligands
• Strong fields ligands (NH3)= more splitting, High value of ∆𝟎
• Weak fields of ligands (H2O)= less splitting, Low value of ∆𝟎
𝒅𝒛𝟐 𝒅𝒙𝟐 −𝒚𝟐
𝒆𝒈
3/5 ∆o
Energy
𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑥𝑧 𝑑𝑥 2 −𝑦2 𝑑𝑧2 2/5 ∆o

Average energy
level 𝒕𝟐𝒈
𝒅𝒙𝒚 𝒅𝒙𝒛 𝒅𝒚𝒛
𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑥𝑧 𝑑𝑥 2 −𝑦2 𝑑𝑧2

Degenerated d-orbitals
In general, ligands can be arranged in a series in the order of increasingfield strength

as given below:
I– < Br– < SCN– < Cl– < S2– < F – < OH– < C2O42– < H2O < NCS–< edta4– < NH3 < en < CN– < CO
Order of increasing field strength
Such a series is termed as spectrochemical series. It is an experimentally determined

series based on the absorption of light by complexes with different ligands.
Let us assign electrons in the d orbitals of metal ion in octahedral coordination

entities.
Obviously, the single d electron occupies one of the lower energies t2g orbitals. In d2
and d3 coordination entities, the d electrons occupy the t2g orbitals singly in
accordance with the Hund’s rule.
For d4 ions, two possible patterns of electron distribution arise:
(i) the fourth electron could either enter the t2g level and pair with an existing
electron, or
(ii) it could avoid paying the price of the pairing energy by occupying the eg level.
Which of these possibilities occurs, depends on the relative magnitude of the
crystal field splitting, ∆o and the pairing energy, P (P represents the energy
required for electron pairing in a single orbital). The two options are
(i) If ∆o < P, the fourth electron enters one of the eg orbitals giving the
3 1
configuration 𝑡2𝑔 𝑒𝑔 . Ligands for which ∆o < P are known as weak field
ligands and form high spin complexes.
(ii) If ∆o > P, it becomes more energetically favourable for the fourth electron
4 0
to occupy a t2g orbital with configuration 𝑡2𝑔 𝑒𝑔 .Ligands which produce this
effect are known as strong field ligands and form low spin complexes.
Calculations show that d4 to d7 coordination entities are more stable for

strong field as compared to weak field cases.
(b) Crystal field splitting in Tetrahedral coordination entities

In tetrahedral coordination entity formation, the d orbital splitting is inverted
and is smaller as compared to the octahedral field splitting.
For the same metal, the same ligands and metal-ligand distances, it can be shown
that ∆t = (4/9) ∆0.
Consequently, the orbital splitting energies are not sufficiently large for forcing
pairing and, therefore, low spin configurations are rarely observed. The ‘g’ subscript is
used for the octahedral and square planar complexes which have centre of symmetry.
Since tetrahedral complexes lack symmetry, ‘g’ subscript is not used with energy
levels

𝒅𝒙𝒚 𝒅𝒚𝒛
𝒕𝟐
𝒅𝒙𝒛∆t
2/5
Energy
𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑥𝑧 𝑑𝑥 2 −𝑦2 𝑑𝑧2 3/5 ∆t
Average energy 𝒅𝒙𝟐 −𝒚𝟐 𝑑𝑧 2

level

Degenerated d-orbitals
3) Colour in Coordination Compounds (LOsH6)

Why transition metals form coloured ions in aqueous solution ?
When Transition metals dissolve in solution, they don't exist as isolated ions but are
surrounded by ligands (in aqueous solutions they're water molecules).
They can form complex ions in solution, due to the fact that water can act as a ligand.
Transition metal ions will always form complex ions when in solution with ligands
Ligands always surround the transition metal ion in a particular geometric way. In
aqueous environments, water will usually surround a transition metal ion with
an octahedral geometry,
These ligands donate a pair of electrons to the positive metal ion in a dative covalent bond.
For example, iron forms [Fe(H2O)6]2+ which is pale green. These ions are called complex
ions.
The transition metals have electrons in their d orbitals, which are electrostastically
repelled by those donated by the ligands. Since d orbitals have different shapes and
orientations, they're not all repelled to the same extent: for an octahedral complex ion,
the ligands are placed at the 6 corners of the octadedron. The dz2 and dx2-y2 are pointing
to those corners and so are repelled a lot. The other three d orbitals don't point directly
towards the ligands and so are repelled less. Therefore, the dz2 and dx2-y2 orbitals are at a
higher energy than the other three, and so an energy gap is created, called d orbital
Transition metal ions are usually coloured because of the absorption of radiation from
visible region of light to promote an electron from a lower energy d-orbital to a higher
energy d-orbital . The energy of excitation corresponds to the frequency of light
absorbed.
Transition metal ions generally possess one or more unpaired electrons. When visible light
falls on a transition metal compound or ion, the unpaired electron present in the lower
energy d-orbital get promoted to high energy d-orbital, called d-d transition, due to the
absorption of visible light. These five d orbitals are split into two or more slightly different
energy levels. Thus the promotion of an electron from the lower to higher of these d-orbitals
just happens to require definite energies within the range of visible region, remaining
wavelength present in the visible region got transmitted. Therefore, transmitted light shows
some colour complementary to the absorbed colour.
One of the most distinctive properties of transition metal complexes is their wide range of
colours.
This means that some of the visible spectrum is being removed from white light as it passes
through the sample, so the light that emerges is no longer white. The colour of the complex
is complementary to that which is absorbed. The complementary colour is the colour
generated from the wavelength left over; if green light is absorbed by the complex, it
appears red.
The following table gives the relationship of the different wavelength absorbed and the
colour observed.
Relationship between the Wavelength of Light absorbed and the Colour observed in some
Coordination Entities
The colour in the coordination compounds can be readily explained in terms of the crystal field
theory. Consider, for example, the complex [Ti(H2O)6]3+, which is violet in colour.
Titanium (Ti – p.no 22): 1s2 2s2 2p6 3s2 3p6 3d2 4s2
Titanium ion (Ti3+ ): 1s2 2s2 2p6 3s2 3p6 3d1
This is an octahedral complex where the single electron (Ti3+ is a 3d1 system) in the metal d
orbital is in the t2g level in the ground state of the complex. The next higher state
available for the electron is the empty eg level. If light corresponding to the energy of blue-
green region is absorbed by the complex, it would excite the electron from t2g level to the eg
level (𝑡2𝑔1 𝑒𝑔0 𝑡2𝑔0 𝑒𝑔1 ).
Consequently, the complex appears purple/violet in colour. The crystal field theory attributes
the colour of the coordination compounds to d-d transition of the electron.
All five 3d orbitals have exactly the same energy level in the isolated gaseous Ti3+ ion.
However, when the Ti3+ ion is surrounded by ligands, the 3d orbitals are no longer
symmetrically arranged. Orbitals closer to the ligands are pushed to a slightly higher energy
level than those orbitals further away.

This splitting of the 3d orbitals in the octahedral [Ti (H2O) 6]3+ ion is shown in the following
figure.
hv
𝒆𝒈
(energy)
Energy
Average energy
level 𝒕𝟐𝒈
Excited state Ti (III) in

Octahedral [Ti(H2O)6]3+
Ground state (stable state) of Ti (III) in

octahedral in octahedral [Ti(H2O)6]3+
In the ground (stable) state, the single d-electron occupies one of the d-orbitals of slightly
lower energy. It is now possible for the Ti3+ ion in [Ti (H2O)6]3+ to absorb sufficient energy for
the 3d-electron to be promoted from a lower to higher 3d- orbitals. The difference in energy
between the two sets of 3d orbitals in [Ti(H2O)6]3+ is relatively small. It coincides with the
wave length for green light. Thus, when aqueous TiCl3 is exposed to white light, it absorbs
photons of green light but transmits those of red and blue light. Hence TiCl3 (aq) appears
purple or violet.
NOTE:
It is important to note that in the absence of ligand, crystal field splitting does
not occur and hence the substance is colourless. For example, removal of water from
[Ti(H2O)6]Cl3 on heating renders it colourless.
Transition of electron in [Ti(H2O)6]3+
Similarly, anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour.

The influence of the ligand on the colour of a complex may be illustrated by considering the
[Ni(H2O)6]2+ complex, which forms when nickel(II) chloride is dissolved in water. If the

didentate ligand, ethane-1,2-diamine(en) is progressively added in the molar ratios en:Ni,

1:1, 2:1, 3:1, the following series of reactions and their associated colour changes occur:
• Thus Cu2+ salts look blue due to the absorption of the red wavelength. Anhydrous cobalt (II)
compounds also absorb red light and appear blue.
Why Zn2+ and Sc3+ ions are colourless (LOsH7)

A transition metal is one that produces stable ions with partially filled d orbitals. Technically,
not all of the periodic table’s d block elements are transition metals according to this
definition. Zinc and scandium, for example, aren’t transition metals under this definition
since Zn2+ have a full d level (no unpaired electrons) while Sc3+ (no unpaired electrons)have
no d electrons.
The colour is shown by only those ions which are having unpaired electrons. If there is no
unpaired electrons then
Different components may give colours that differ from one another. Furthermore, differing
charges of the same transition metal can produce distinct hues. Another consideration is the
ligand’s chemical makeup. A metal ion with the same charge can create a varied hue
depending on the ligand to which it binds.
Coordination Number & Shape of Complex (SLOs H8)

As the oxidation state of the metal increases, the d-orbital splitting increases, hence Δ0 or the
Δt increases. So the energy of the electronic transition will change. This is why the change in
the oxidation state of the metal will change the color of the complex.
How do you determine the shape of a transition metal complex?
Complex ions are molecules with a transition metal or its ion at the centre, surrounded by
other molecules called ligands. Ligands determine the shapes of complex ions by forming
coordinate bonds.
Transition metal ions have a partially filled 3d sublevel. Ligands form coordinate bonds when
an orbital that contains a lone pair of electrons overlaps with a vacant orbital on the metal ion.
In other words, the metal acts as a Lewis acid by accepting a pair of electrons, and the ligand
acts as a Lewis base by donating an electron pair.
When it forms an Al3+ ion, its electronic structure is now 1s2 2s2 2p6, leaving all orbitals in the
3rd level empty. Al3+ can now accept lone pairs of electrons from a molecule/ion to stabilise it.
In the example below, Al3+ accepts six lone pairs from six water molecules.
We write the formula for this complex as [ Al (H2O)6 ]3+. Six water ligands each give the
aluminium ion one lone pair of electrons. So, we say the complex [Al (H2O)6 ]3+ has a
coordination number of 6.
Coordination number tells us the number of coordinate bonds in a complex ion.
Coordination numbers also determine the shape of complex ions.

Tetrahedral complex ions
Tetrahedral complexes have four coordinate bonds with bond angles of 109.5º. Large ligands
like Cl- form tetrahedral complexes.
Two examples of tetrahedral complexes are copper chloride [CuCl4]2-, and cobalt chloride
[CoCl4]2-, shown below.
Notice how four Cl- ions form a bond with the central metal ion. Both Cu (II) and Co (II) have a
2+ charge. Each Cl ion carries a 1- charge, thus this gives the overall charge of 2- on both
complex ions.
(4 X Cl- = 4- ; 4- + 2+ = 2- overall charge)
Octahedral complex ions

Octahedral complexes form when there are six coordinate bonds formed around the central
metal. They have a bond angle of 900.
Small ligands like H2O or NH3 form octahedral complexes. A small ligand like water or
ammonia leaves space for more ligands to fit around the complex ion. On the other hand,
large ligands like chlorine leave space only for four ligands.
There are many ways these six coordinate bonds can be formed.
• Six small monodentate ligands - each ligand forms one coordinate bond with the central
metal. H2O and NH3 are examples of ligands that form one coordinate bond.
• Three bidentate ligands - each ligand forms two coordinate bonds with the central
metal. The oxalate (ethanedioate) ion (ox) or ethylenediamine (en) are examples of an
ion and molecule respectively, that can donate two lone pairs of electrons and form two
coordinate bonds.
• One multidentate ligand - one ion/molecule can form three or more coordinate bonds
to the metal ion. EDTA4- is the most common example of a multidentate ligand.
In addition to the two shapes we have looked at, linear and square-shaped complexes can also
form. Let us consider these now.
Linear complex ions
Linear complex ions form when there are two coordinate bonds. They have a bond angle of
180°.
A common example of a linear complex ion is diamminesilver(I) [Ag(NH₃)₂]⁺, which is used in

Tollens’ reagent.
Square planar complexes
Square planar complexes have four coordinate bonds too! Unlike tetrahedral complexes, they
have a bond angle of 90º.
An early drug used in the treatment of cancer, cis-platin, forms a square planar complex. It has
the platinum ion, Pt2+, as its central ion, and two ammonia molecules and two chloride ions as
ligands.

Ligand Substitution: Change in Co-ordination Number (SLOs H8)

When water molecules are replaced by larger ligands, for example chloride ions, there is a
change in co-ordination number and shape. This is because only four chloride ions can fit
around the central transition metal ion. The complex formed is tetrahedral in shape.
Substitution by Water Ligands 

If you dissolve any transition metal salt in water, the central transition metal atom or ion
becomes surrounded by water ligands.
Complexes with water are called metal-aqua complex ions. They are octahedral and have a
co-ordination number of 6.
For example:
Solutions containing aqueous complexes have particular colours which can help to identify
which transition metal is present.
Substitution by Other Ligands 

These water ligands can be replaced by other ligands. This occurs because:
• Other ligands form stronger co-ordinate bonds than water

• Other ligands are present in higher concentrations
Complete and Incomplete Substitution 

Complete ligand substitution occurs when all the original ligands are replaced.
Incomplete ligand substitution occurs when only some of the original ligands are replaced.
Incomplete ligand substitution occurs if the partially substituted complex is energetically more
stable than either the original complex or completely substituted complex.
Coordination compounds as catalyst

Coordination compounds are used as both homogenous and heterogeneous catalysts. For
example, Wilkinson catalyst [(Ph3P)3RhCl][(Ph 3P)3RhCl] is employed in the hydrogenation
of alkenes.
1. The complex, [(C2H5)4Pb][(C2H5)4Pb] is used as an antiknock.
2. A complex ion, [Ag(S2O3)2]3–[Ag(S2O3)2]3– is formed when a developed photographic
film is washed with hypo solution. The excess AgBr present dissolves to form the
complex ion.
3. A catalyst comprising a mixture of an organo-metallic compound, e.g.,
triethylaluminum, and a transition-metal compound, e.g., titanium tetrachloride.
Often called Ziegler or Ziegler–Natta catalysts, they are used in polymerizing olefins
and dienes.
introducing complex ions - ligands and bonding (chemguide.co.uk)

Transition Elements & Cordination Chemistry (NCUK)

Uploaded by

Copyright:

Available Formats

Transition Elements & Cordination Chemistry (NCUK)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Transition Elements & Cordination Chemistry (NCUK)

Uploaded by

Copyright:

Available Formats

NCUK -Chemistry Department Page:1

Topic H- Transition Metals and Coordination Chemistry

Definition of the Transition Metals:

Kings International School Yangon, Myanmar

1St Transition Series ( 3d1– 104s1–2) : Los H1

General Electronic Configuration of d-Block Elements

Kings International School Yangon, Myanmar

Properties of Transition Metals

1) Transition metals can have variable oxidation states.

Kings International School Yangon, Myanmar

1) Variable oxidation states

1St Transition Series (Oxidation States)

2) Formation of complex compounds

Kings International School Yangon, Myanmar

These compounds are also called coordination complexes.

Colour Formula Solution Conductivity

Kings International School Yangon, Myanmar

Werner in 1898, propounded his theory of coordination compounds.

Moles of AgCl precipitated

What are the coordination compounds? (SLOsH3)

Kings International School Yangon, Myanmar

Double salt coordination compounds

Kings International School Yangon, Myanmar

Some important terms pertaining to Coordination compounds

Simple ligands include water, ammonia, and chloride ions.

Kings International School Yangon, Myanmar

When a ligand is bound to a metal ion through a single donor

When a when several donor atoms are

1. Unidentate (one donor site) or Monodentate

Kings International School Yangon, Myanmar

Ligand Charge Donor atom Type Name given in the

COO¯ Two oxygen

NH2 One nitrogen Bidentate

Kings International School Yangon, Myanmar

d) Coordination number  (SLOsH2, SLOs 8)

(e) Coordination sphere 

(f) Coordination polyhedron 

Kings International School Yangon, Myanmar

The following figure shows the shapes of different coordination polyhedral.

(g) Oxidation number of central atom 

(h) Homoleptic and heteroleptic complexes

Shape of complexes (SLOs H5)

In complexes with coordination number 6, the ligands usually occupy octahedral

(i) Shape of the complexes with coordination number two:

Kings International School Yangon, Myanmar

Tetrahedral Square planar

(iii) Shape of the complexes with coordination number six:

Bonding in Coordination Compounds 

Limitations of Valence Bond Theory 

(i) It involves a number of assumptions.

Crystal field splitting:

Kings International School Yangon, Myanmar

Degenerate orbitals: Orbitals having same energy

The important point of CFT:

(a) Crystal field splitting in octahedral coordination entities

Kings International School Yangon, Myanmar

• ∆0 = Crystal field Splitting energy

𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑥𝑧 𝑑𝑥 2 −𝑦2 𝑑𝑧2 2/5 ∆o

𝑑𝑥𝑦 𝑑𝑦𝑧 𝑑𝑥𝑧 𝑑𝑥 2 −𝑦2 𝑑𝑧2