CHM 211: INTRODUCTION TO TRANSITION METAL CHEMISTRY

The periodic table is divided into four blocks: s. p. d and f blocks. The elements of the s and p
block together are called representative elements; in these elements, electrons fill in the
outermost ns or np subshell. The elements of the d and f blocks are called transition elements.
The transition elements are sandwiched between the s and p block elements. All the elements
are metals. Transition metals are also known as transition elements or d-block elements. As the
name implies, the chemistry of this group is determined by the extent to which the d-electron
suborbital levels are filled.
DEFINITION
A transition metal is one that forms one or more stable ions which have incompletely filled d
orbitals. Transition elements (also known as transition metals) are elements that have partially
filled d orbitals.
IUPAC defines transition elements as an element having a d subshell that is partially filled with
electrons, or an element that has the ability to form stable cations with an incompletely filled d
orbital.
Transition elements can also be defined as elements that have partly/partially filled d or f
subshells in any of their occurring oxidation states.
Their electronic configuration is unique in that they have valence electrons in two different
subshells ns and (n-1) d subshells

LOCATION
The transition elements or transition metals occupy the short columns in the center of the
periodic table, between Group 2A and Group 3A.  They are sometimes called the d-block
elements since the d-orbitals are being filled in in this region  

Transition elements are categorized into two:

i. main transition elements (d block)

ii. Inner transition elements (f block)

The main transition elements are called the d-block elements. The d-block elements have
partly filled subshells in any of their occurring oxidation states. It consists of three series, each
consisting of ten elements

i. The first row is called the 3d series elements and consists of ten elements from Sc
(Z=21) to Zinc (Z=30). They have their valence electrons in (n-1) d i.e. 3d and ns i.e. 4s
orbitals. The general electronic configuration of 3d series elements is [Ar]3d 1-10 4s1-2
ii. The second row is called the 4d series elements and consists of ten elements from Y
(Z=39) to Cd (Z=48). They have their valence electrons in (n-1) d i.e. 4d and ns i.e. 5s
orbitals. The general electronic configuration is [Kr] 4d1-10 5s1-2

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iii. The third-row elements are called the 5d series. It starts from La[Z=57) and ends with
Hg (Z=80). They have their valence electrons in (n-1) d i.e. 5d and ns i.e. 6s orbitals.

The inner transition elements are referred to as the f- block. They comprise lanthanides; the
elements that follow lanthanum (Z=57) and actinides the elements that follow actinium (Z=89.
They provide a transition in the 6th and 7th row of the periodic table which separates the s-block
and the d-block elements. In the f-block elements, the 4f and 5f orbitals are filled. Each of the
f-block comprises fourteen elements.

In the periodic table, the period 4 transition metals are scandium (Sc), titanium (Ti), vanadium
(V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc
(Zn).  The period 5 transition metals are yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum
(Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and cadmium
(Cd).   The period 6 transition metals are lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten
(W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg).  The
period 7 transition metals are the naturally-occurring actinium (Ac), and the artificially
produced elements rutherfordium (Rf), dubnium (Db), seaborgium (Sg), bohrium (Bh), hassium
(Hs), meitnerium (Mt), darmstadtium (Ds), roentgenium (Rg), and the as-yet-unnamed
ununbiium (Uub).

All of the transition metals in their elemental forms are malleable and ductile (except for
mercury, which is a liquid at room temperature), and are good conductors of heat and
electricity.  Many of the transition metal ions have characteristic colors associated with them,
and many have biological and industrial significance.

Electronic Configuration of Transition Elements

In the transition metals, the five d orbitals are being filled in, and the elements, in general, have
electron configurations of (n-1) d1-10 ns2, although there are some exceptions when electrons
are shuffled around to produce half-filled or filled d subshells.  Many of the transition metals
can lose two or three electrons, forming cations with charges of 2 + or 3+, but there are some
that form 1+ charges, and some which form much higher charges.
The list of the first two rows of transition elements with their corresponding electronic
configurations is tabulated below. It can be noted that in some of these elements, the
configuration of electrons corresponds to (n-1)d 5 ns1 or (n-1)d10 ns1. This is because of the
stability provided by the half-filled or completely-filled electron orbitals. Half-filled and
completely-filled subshells have extra stability due to symmetry and high exchange energy. The
stability makes the configurations have a lower energy level.
When transition metals form ions, electrons are lost from the 4s subshells rather than the 3d
subshell

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 Transition Elements Atomic Number Electronic Configuration

Sc 21 [Ar] 3d1 4s2

Ti 22 [Ar] 3d2 4s2

V 23 [Ar] 3d3 4s2

Cr 24 [Ar] 3d5 4s1

Mn 25 [Ar] 3d5 4s2

Fe 26 [Ar] 3d6 4s2

Co 27 [Ar] 3d7 4s2

Ni 28 [Ar] 3d8 4s2

Cu 29 [Ar] 3d10 4s1

Zn 30 [Ar] 3d10 4s2

General Properties of Transition Elements

The elements zinc, cadmium, and mercury are not considered transition elements since their
electronic configurations are different from other transition metals. However, the rest of the d-
block elements are somewhat similar in properties and this similarity can be observed along
each specific row of the periodic table. These properties of the transition elements are listed
below.

 These elements form coloured compounds and ions. This colour is explained by the d-d
transition of electrons.
 There is a relatively low gap in energy between the possible oxidation states of these
elements. The transition elements, therefore, exhibit many oxidation states.

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 Many paramagnetic compounds are formed by these elements, because of the unpaired
electrons in the d orbital.
 A large variety of ligands can bind themselves to these elements. Due to this, a wide
variety of stable complexes are formed by transition elements.
 These elements have a large ratio of charge to radius.
 Transition metals tend to be hard and they have relatively high densities when
compared to other elements.
 The boiling points and the melting points of these elements are high, due to the
participation of the delocalized d electrons in metallic bonding.
 This metallic bonding of the delocalized d electrons also causes the transition elements
to be good conductors of electricity.

Physical properties

Transition elements are all metals with high melting and boiling points

They are all hard and dense

They have atoms/ions with much smaller sizes when compared to their corresponding s and
p block elements

Atomic size and ionic size

The atomic size decreases from left to right across the period in the transition series until
near the end when the size slightly increases. In moving across the series of metals from
scandium to zinc, the nuclear charge increases but electrons are being added to an inner d
subshell. These inner d electrons shield the 4s outer electrons from the increasing nuclear
charge much more effectively than outer shell electrons can shield each other.
Consequently, the atomic radii decrease much less rapidly. Near the end of the series, the
size slightly increases because the d electrons are so large in number that they repel each
other and the electron cloud slightly expands.

On moving down the group, atomic size usually increases because an extra shell of electrons
is added. In group 3, there is a regular increase in size from Sc < Y < La. But in groups, 4 to
group 12, the increase in size from 3d series to 4d series is 0.1Å to 0.2 Å, but 5d series
elements have the almost same size as 4d series elements. E.g in group 4, Zr and Hf have a
comparable size (Zr =1.45Å, Hf = 1.44 Å). In group 5, Nb and Ta have the same size, because
between La and Hf are fourteen lanthanides I from 58Ce to 71 Lu) in which the filling of
electrons takes place in the antepenultimate 4f subshell. The 4f subshell has the poorest
shielding effect, hence, the electrons are pulled inward towards the nucleus and the size
decreases. The regular decrease in size from Ce to Lu as the atomic number increases are
known as Lanthanide contraction.

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All 5d series elements from Hf to Hg have fully filled 4f subshells. Due to the poorest
shielding effect of 4f, electrons are drawn to the nucleus and the size decreases to such an
extent that it becomes comparable to the 4d series.

Metallic Character

All the metals have only one or two s electrons in the outermost shell and these are readily
given up to form positive ions. Therefore, all transition elements are metallic elements.
They exhibit good mechanical properties i.e. they are hard, malleable, and ductile.
Transition metals exist in all three types of structure i.e face centred cubic (fcc), body
centred cubic (bcc), and hexagonal close packing (hcp). These metals, therefore, have high
coordination numbers of 12 in hcp and fcc and 8 in bcc.

Melting point and boiling point

Transition metals have high melting and boiling points. They typically melt above 1000 oc.
The high melting points are attributed to strong interatomic bonding (metallic bonding)
which involves the participation of both (n=1)d and ns electrons. The number of electrons
available for metallic bonding increases from Sc to Cr, hence, the melting point also
increases. Manganese (Mn) has 3d5 4s2 configuration which is very stable and symmetrical.
As a result, the electrons have very less tendency to participate in metallic bonding. Hence
manganese has an exceptionally low melting point Mn to Fe, melting point increases and
after Fe, there is regular decrease because number of unpaired electrons in 3d subshell
decreases the strength of metallic bond; hence the melting point decreases. Zinc (Zn) has
the lowest melting point in the 3d series. The melting point decreases down the groups. Zn,
Cd, Hg have exceptionally low melting points due to fully-filled d subshell.

Chemical properties

Transition elements show the following chemical properties:

i. Variable oxidation states

ii. Complex ion/compound fornmation
iii. Cloured ion/compound formation
iv. Formation of interstitial compounds
v. Catalytic properties
vi. Paramagnetism

Variable oxidation states

The energy difference between the 4s and 3d orbitals is very small hence the electrons in
both the 3d and 4s levels have similar energy. This means that one particular element can
form ions of roughly the same stability by losing different number of electrons. Thus all the

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transition metals form two or more oxidation states in their compounds but Sc and Zn show
only one oxidation state: Sc3+ and Zn2+

 Note
The common oxidation states for each element include +2 or +3 or both. +3 states
are relatively common at the beginning of the series and + 2 oxidation states are
more common toward the end of the series.
 The highest oxidation states from Sc to Mn correspond to all involvement of all
electrons outside the argon noble gas core (4 for Ti, 5 for V, 6 for Cr, and 7 for Mn).
After this the increasing nuclear charge binds the d electrons more strongly, so one
of the more important oxidation states is that which involves the weakly held
electrons in the outer 4s shell only (2 for Fe, 2 for Co, 2 for Ni and 1 for Cu)
 Mn shows the highest oxidation state of +7 (e.g. in KMnO7)
 Transition metals exhibit their highest oxidation states in compounds with fluorine

Sc 3

Ti 2, 3, 4

V 2, 3, 4, 5

Cr 1, 2, 3, 4, 5, 6

Mn 2, 3, 4, 5, 6, 7,

Fe 2, 3, 4, 5, 6

Co 2, 3, 4, 5

Ni 2, 3, 4

Cu 1, 2, 3

Zn 2

Ti, V, Cr, and Mn never form simple ions in their highest oxidation state since this would
result in ions of extremely high charge density; hence the compounds of these elements in
their highest oxidation states are either covalently bonded (e.g TiO 2, V2O5, CrO3, Mn2O7) or
contain complex ions (e.g VO3-, CrO42-, MnO4-)

For a given element, the higher oxidation states are:

 Covalent
 Acidic and

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  Strongly oxidizing

With carbonyls, the metal shows a zero oxidation state e.g Ni(CO) 4
Magnetic properties

Most of the transition metal ions are paramagnetic. Para magnetism arises due to the presence
of unpaired electrons. Each such electrons have a magnetic moment associated with its spin
angular momentum and orbital angular momentum. For 3d series elements, the contribution of
the orbital angular momentum is zero so they have only spin angular momentum. Magnetic
moment increases with an increasing number of unpaired electrons

Substances show two different types of magnetic behaviour when subjected to an applied
magnetic field:
Paramagnetic substances are attracted by the applied magnetic field due to the presence of
unpaired electrons.
Ferromagnetic substances are strongly attracted by the magnetic field much more than
paramagnetic substances.
Diamagnetic substances have all their electrons paired and are repelled by the applied
magnetic field.

Complex ion/compound formation

Complex ions are compounds composed of a central metal ion surrounded by ions, atoms, or
molecules called ligands. Transition elements have more tendency to form complexes than s
and p block elements. They form complexes with the groups(ligands) which are able to donate
electron pairs. Their tendency to form complexes is due to two reasons:
i. small size and high nuclear charge. The high charge density constitutes a strong electrostatic
force of attraction with the ligands thereby increasing the stability of the complex.
ii. Availability of low-lying vacant d-orbitals of suitable energy to accommodate lone pairs of
electrons donated by the ligands

Catalytic properties

Most of the transition metals and their compounds are used as catalysts. Transition metals
show catalytic behaviour due to the following reasons:
i. presence of vacant d-orbitals.
Their partly filled empty d-orbitals provide surface area for the reactant molecule. They
combine with the reactant molecules to form transition states and lower their activation
energy.
ii. Ability to exhibit variable oxidation states/valencies. The ability of transition metals to be in a
variety of oxidation states helps in giving electrons to reactants; they form complexes and
lower their energy.
iii. Tendency to form complex compounds.
catalysis by metal compounds results from their ability to provide low-energy pathways for

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 either by a change in oxidation state or by the formation of appropriate intermediates.
reactions
During the course of the reaction, the catalyst undergoes changes in oxidation state. It is
however regenerated in its original form when the reactants from the products. Example:

Ti in TiCl4/Al2(C2H5)6 Ziegler Natta catalyst in the conversion of ethene to polyethylene

V V2O5 contact process in the conversion of SO2 (Sulphur iv oxide) to SO3 (Sulphur vi oxide)

Fe Fe/Fe2O3 in Haber process

Pt in Ostwald process of conversion of NO (nitrogen ii oxide) to nitrogen iv oxide NO 2 and

then to HNO3 nitric acid.

Alloy formation

All transition elements are metals and have a lattice structure. Due to their comparable size,
one metal can displace another metal in the crystal lattice to form alloys. They are miscible with
one another in the molten state, on cooling they form alloys e.g. brass (CU, Zn); alnico (Al, Ni,
Co) Stainless steel (Fe, Cr, Ni).

Interstitial compound

Interstitial compounds are those which are formed when small atoms like H, B, N, and C are
trapped inside the crystal lattice of metals. They are usually non-stoichiometric and are neither
typically ionic nor covalent. interstitial compounds are well-known as transition metal
compounds due to their closed crystalline structure with voids in them. These voids are called
interstice, when these electronegative elements are trapped in the interstices of transition
metals crystal lattice, interstitial compounds are formed. E.g TiCMn4N, Fe3H, TiH2. It is
however noted that the formula of interstitial compounds does not correspond to any normal
oxidation state of the metal e.g. VH0.56, TiH1.07
Interstitial compounds have the following physical and chemical properties:

i. High melting point higher than those of pure metals

ii. Are very hard e.g. some borides have hardness comparable to diamond

iii. Retain metallic conductivity

iv. Are chemically inert

Colour formation

Most transition metal compounds are coloured. The colour formation is related to the
presence of unpaired electrons/incompletely filled d-orbitals in the transition metal ions. All

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 Zn2+ and Sc3+ compounds are white die to the absence of any unpaired electron. Colour
formation is associated with the absorption of electromagnetic radiation in visible light
which brings about transition/excitation of electrons between the d orbitals of transition
metals called the *d-d* transition spectra. The unpaired electrons in the lower energy d
orbital get promoted /excited to high energy d-orbital due to the absorption of visible light.
Since the energy involved in the *d-d* transition is quantized, only a definite wavelength
gets absorbed remaining wavelengths present in the visible region get transmitted.
Therefore, transmitted light shows some colour complimentary to the absorbed colour.

CRYSTAL FIELD THEORY

Crystal field theory describes the net change in crystal energy resulting from the orientation
of d orbitals of a transition metal cation inside a coordinating group of anions also called
ligands. A major feature of transition metals is their tendency to form complexes. A complex
may be considered as consisting of a central metal atom or ion surrounded by a number of
ligands. The interaction between these ligands with the central metal atom or ion is subject
to crystal field theory.

Crystal field theory treats the interaction of metal ions and ligands as a purely electrostatic
phenomenon where the ligands are considered as point charges in the vicinity of the atomic
orbitals of the central atom. Development and extension of crystal field theory considered
the partly covalent nature of bonds between the ligand and metal atom mainly through the
application of molecular orbital theory. Crystal field theory is often termed ligand field
theory.

The theory described the metal-ligand bond as an ionic bond arising purely from the
electrostatic interactions between the metal ions and ligands. It considers anions as point
charges and neutral molecules as dipoles.
When transition metals are not bonded to any ligand, their d orbitals are degenerate that is
they have the same energy. When they start bonding with other ligands, due to different
symmetries of the d orbitals and the inductive effect of the ligands on the electrons, the d
orbitals split apart and become non-degenerate.

Important features of Crystal field theory:

•The interactions between the metal ion and the ligands are purely electrostatic (ionic).
•The ligands are regarded as point charges
•If the ligand is negatively charged: ion-ion interaction. If the ligand is neutral: ion-dipole
interaction
•The electrons on the metal are under repulsive from those on the ligands
•The electrons on metal occupy those d-orbitals farthest away from the direction of approach
of ligands
•The 5d orbitals in an isolated gaseous metal are degenerate.

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•If a spherically symmetric field of negative charges is placed around the metal, these orbitals
remain degenerate, but all of them are raised in energy as a result of the repulsion between the
negative charges on the ligands and the d orbitals

The d-orbitals are fivefold degenerate in a free gaseous metal ion. If a spherically symmetric
field of negative ligand filed charge is imposed on a central metal ion, the d-orbitals will remain
degenerate but followed by some changes in the energy of the free ion.

A summary of the interactions is given below.

Crystal Field Splitting

High Spin and Low Spin

The complexion with the greater number of unpaired electrons is known as the high spin
complex, the low spin complex contains the lesser number of unpaired electrons. High spin
complexes are expected with weak field ligands whereas the crystal field splitting energy is
small Δ. The opposite applies to the low spin complexes in which strong field ligands cause
maximum pairing of electrons in the set of three t2 atomic orbitals due to large Δo.

 High spin – Maximum number of unpaired electrons.

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  Low spin – Minimum number of unpaired electrons.

Example: [Co(CN)6]3- & [CoF6]3-

Crystal Field Splitting in Octahedral Complex 

 In the case of an octahedral coordination compound having six ligands surrounding the
metal atom/ion, we observe repulsion between the electrons in d orbitals and ligand
electrons.
 This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point
towards the axes along the direction of the ligand.
 Hence, they have higher energy than average energy in the spherical crystal field.
 On the other hand, dxy, dyz, and dxz orbitals experience lower repulsions as they are
directed between the axes.
 Hence, these three orbitals have less energy than the average energy in the spherical
crystal field.

Thus, the repulsions in the octahedral coordination compound yield two energy levels:

 t2g– set of three orbitals (dxy, dyz and dxz) with lower energy
 eg – set of two orbitals (dx2-y2 and dz2) with higher energy

Crystal Field Splitting in Octahedral Complex

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This splitting of degenerate level in the presence of ligand is known as crystal field splitting. The
difference between the energy of t2g and eg level is denoted by “Δo” (subscript o stands for
octahedral). Some ligands tend to produce strong fields thereby causing large crystal field
splitting whereas some ligands tend to produce weak fields thereby causing small crystal field
splitting.

Crystal Field Splitting in Tetrahedral Complex 

The splitting of fivefold degenerate d orbitals of the metal ion into two levels in a tetrahedral
crystal field is the representation of two sets of orbitals as T d. The electrons in dx2-y2 and dz2
orbitals are less repelled by the ligands than the electrons present in d xy, dyz, and dxz orbitals. As
a result, the energy of dxy, dyz, and dxz orbital sets are raised while that of the dx2-y2 and dz2
orbitals are lowered.

 There are only four ligands in Td complexes and therefore the total negative charge of
four ligands and hence the ligand field is less than that of six ligands.
 The direction of the orbitals does not coincide with the directions of the ligands
approach to the metal ion.

Crystal Field Splitting in Tetrahedral Complex

Thus, the repulsions in tetrahedral coordination compound yield two energy levels:

 t2– set of three orbitals (dxy, dyz and dxz) with higher energy
 ℮.g – set of two orbitals (dx2-y2 and dz2) with lower energy

The crystal field splitting in a tetrahedral complex is intrinsically smaller in an octahedral field
because there are only two-thirds as many ligands and they have a less direct effect of the d
orbitals. The relative stabilizing effect of the ℮.g set will be -6Dq and the destabilizing effect of
t2 set will be +4Dq

Crystal Field Stabilization Energy

In a chemical environment, the energy levels generally split as directed by the symmetry of the
local field surrounding the metal ion. The energy difference between the eg and t 2g levels is

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given as 10Dq. It states that each electron that goes into the lower t2g level stabilizes the system
by an amount of -4Dq and the electron that goes into eg level destabilizes the system by +6Dq.
That is the t2g is lowered by 4Dq and the eg level is raised by +6Dq.

For example, the net change in energy for d5 and d10 systems will be zero as shown below.

d5 :- 3(-4Dq) + 2(+6Dq) = -12Dq + 12Dq = 0

d10 :- 6(-4Dq) + 4(+6Dq) = -24Dq + 24Dq = 0

The decrease in energy caused by the splitting of the energy levels is called the “Ligand Field
Stabilization Energy (LFSE)”. 

Thus, the crystal field splitting depends on the field produced by the ligand and the charge on
the metal ion. An experimentally determined series based on the absorption of light by
coordination compound with different ligands known as spectrochemical series has been
proposed. The spectrochemical series arranges ligands in order of their field strength:

I- < Br- < S2- < SCN- < Cl- < N3-, F- < urea, OH- < C2O42-(ox), O2- <H2O < NCS- < py, NH3 < en < bpy,
phen < NO2-< CH3-, C6H5-< CN- < CO.

This series shows that the value of the series also increases from left to right.
The order of field strength of the common ligands shown above is independent of the
nature of the central metal ion and the geometry of the complex.
Although the spectrochemical series and other trends described in this section allow one to
rationalized differences in spectra and permit some predictability, they present serious
difficulties in the interpretation of crystal field theory. If the splitting of the d orbitals resulted
simply from the effect of point charges (ions or dipoles), one should expect that anionic ligands
would exert the greatest effect. On the contrary, most anionic ligands lie at the low end of the
spectrochemical series. Furthermore, OH- lies below the neutral H2O molecule and NH3
produces a greater splitting than H2O, although the dipole moment in the reverse order

Filling of d-orbitals takes place in the following manner; the first three electrons are arranged in
the t2g level as per Hund’s rule. The fourth electron can either enter into the t2g level giving a
configuration of t2g4eg0 or can enter the eg orbital giving a configuration of t2g3eg1. This depends
on two parameters magnitude of crystal field splitting, Δo, and pairing energy, P. The
possibilities of the two cases can better be explained as

 Δo > P – Electron enters in the t2g level giving a configuration of t2g4eg0. Ligands producing
this configuration are known as strong field ligands and form low-spin complexes.
 Δo < P – Electron enters in the eg level giving a configuration of t2g3eg1. Ligands producing
this configuration are known as weak field ligands and form high-spin complexes.

Factors Affecting the Magnitude of ∆o

1- Oxidation state of the metal ion

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 The magnitude of increases with increasing ionic charge on the central metal ion.
The cations from atoms of the same transition series and having the same oxidation
the state has almost the same value but the cation with a higher oxidation state has a
a larger value than that with a lower oxidation state
This effect is probably due to the fact that the central ion with a higher oxidation state
(higher charge) will polarize the ligands more effectively and thus the ligands would
approach such a cation more closely than they can do the cation of lower oxidation
state, resulting in larger splitting.
2- Nature of the metal ion
Significant differences also occur for analogous complexes within a given group,
the trend being 3d < 4d <5d.
e.g In progressing from Cr to Mo or Co to Rh, the value increases by as much as
50%. Likewise, the values for Ir complexes are some 25% greater than for Rh
complexes.
An important result of this trend is that complexes of the second and third transition
series has a much greater tendency to be low spin than do complexes of the first
transition series.
3- Number and geometry of the ligands
The point-charge model predicts that a tetrahedral complex will be only about
50% as large as for an octahedral complex, all other factors being equal. This approximate
relationship is observed for VCl4 and [VCl6]2- , as well as for [Co(NH3)4]2+
and [Co(NH3)6]2+. (The crystal field splitting in a tetrahedral field is smaller than that in
an octahedral field. For the same metal ion, ligands, and metal-ligand distances,
( t = 4/9 ∆o.)
4- Nature of the ligands
The magnitude of ∆o varies from strong to weak ligands. Strong ligands are those which
exert a strong field on the central metal ion and hence have higher splitting power
consequently relatively lower splitting power. Thus, strong ligands (e.g. CN -) give larger
value of ∆o and weak ligands (e.g. F-) yield a smaller value of ∆o.
Based on similar data of the absorption spectra for a wide variety of complexes, it is
possible to list ligands in order of increasing field strength in a spectrochemical series.
The common ligands can be arranged in the order of their increasing splitting power to
cause d-splitting. This series is called the spectrochemical series.

LIMITATIONS OF CFT
1. CFT considers the splitting of d- orbital but it does not consider the
splitting of other orbitals in the ligand field environment.
2. CFT can’t explain how certain ligands have more splitting
power/ability while certain other ligands have very low splitting
ability.
3. According to the CFT metal-ligand bond have 100% ionic character
but from the various experiment it was found that metal-ligand bonds
have a certain extent of covalence with the ionic character.

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APPLICATIONS OF THE CFT
The following properties of transition metal complexes ca will be
explained on the basis of CFT.
1. According to the CFT if the split set d-orbitals of the CMI present in
the complexes containing the unpaired e- then the complex will be called
as paramagnetic in rapture while if the split set of d-orbitals of the
CMI does not contain the unpaid e- then the complex will be called as
diamagnetic in nature.

Example:
(I) [Co (F)6]-3 ion
Configuration of Co = 3d7, 4S2
The oxidation state of CO = +3
Configuration of CO+3 = 3d6
According to CFT:

℮g

3d6

t 2g

Since the split set of d- orbital containing 4 unpaired e- due to which

the complex ion [Co (F)6]-3 ion will be paramagnetic in nature and

according to CFT .
(II) [Co (NH3)6]+3 ion
Configuration of Co = 3d7 4S2
Oxidation State of Co = +3
Configuration of CO+3 = 3d6
According to CFT:

℮g

3d6

t2g

Biological functions of transition metals

Several transition metals are important to the chemistry of living systems, the most familiar
examples being iron, cobalt, copper, and molybdenum. Iron is by far the most widespread and

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important transition metal that has a function in living systems; proteins containing iron
participate in two main processes, oxygen transport and electron transfer (i.e., oxidation–
reduction) reactions. There are also a number of substances that act to store and transport iron
itself.
Though cobalt is understood to be an essential trace element in animal nutrition, the only
detailed chemical knowledge of its biochemical action has to do with vitamin B 12 and related
coenzymes. These molecules contain one atom of cobalt bound in a macrocyclic ring (i.e., one
consisting of many atoms) called corrin, which is similar to a porphyrin ring. Copper is found in
both plants and animals, and numerous copper-containing proteins have been isolated. The
blood of many lower animals, such as mollusks, cephalopods, gastropods, and decapods,
contains respiratory proteins called hemocyanins, which contain copper atoms (but no heme)
and appear to bind one oxygen molecule per two copper atoms. Human serum contains a
glycoprotein called ceruloplasmin, the molecule of which contains eight copper atoms; its
biological function is still uncertain. Other proteins, called cerebrocuprein, erythrocuprein, and
hepatocuprein, that are found in the mammalian brain, erythrocytes, and liver, respectively,
contain about 60 percent of the total copper in those tissues; their functions are still unknown.
There are a number of copper-containing enzymes; examples are (1) ascorbic acid oxidase (an
oxidase is an oxidizing enzyme), which contains eight atoms of copper per molecule; it is widely
distributed in plants and microorganisms; (2) cytochrome oxidase, which contains heme and
copper in a 1:1 ratio; (3) tyrosinases, which catalyze the formation of melanin (brownish-black
pigments occurring in hair, skin, and retina of higher animals) and were the first enzymes in
which copper was shown to be essential to function.

Vanadium occurs widely in petroleum, and can be isolated as porphyrin complexes, the origin
of which is not known. Vanadium is present in high concentrations in blood cells (vanadocytes)
of certain ascidians (sea squirts), apparently in a curious, complex, and poorly understood
protein-containing substance called hemovanadin, thought to serve in oxygen transport.
Molybdenum is believed to be a necessary trace element in animal diets, but its function and
the minimum levels have not been established. Nitrogen-fixing bacteria utilize enzymes that
contain both molybdenum and iron. One such enzyme, or at least a part of it that has been
isolated in the crystalline state, contains two atoms of molybdenum and 40 atoms of iron. This
protein in association with another, which contains only iron, can catalyze the reduction
of nitrogen gas to nitrogen compounds.

Efforts to understand the function of transition metals in biological systems have led to the
growth of the field of bioinorganic chemistry.

COORDINATION COMPOUNDS
Coordination compounds are a major feature of the chemistry of over half the
elements. Coordination compounds have important roles as industrial catalysts in controlling
reactivity, and they are essential in biochemical processes.

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 Coordination chemistry emerged from the work of Alfred Werner, a Swiss chemist who
examined different compounds composed of cobalt (III) chloride and ammonia. Upon the
addition of hydrochloric acid, Werner observed that ammonia could not be completely
removed. He then proposed that the ammonia must be bound more tightly to the central
cobalt ion. However, when aqueous silver nitrate was added, one of the products formed was
solid silver chloride. The amount of silver chloride formed was related to the number of
ammonia molecules bound to the cobalt (III) chloride. For example, when silver nitrate was
added to CoCl3·6NH3, all three chlorides were converted to silver chloride. However, when silver
nitrate was added to CoCl3·5NH3, only 2 of the 3 chlorides formed silver chloride. When
CoCl3·4NH3 was treated with silver nitrate, one of the three chlorides precipitated as silver
chloride.

The resulting observations suggested the formation of complex or coordination compounds. In

the inner coordination sphere, which is also referred to as the first sphere, ligands are directly
bound to the central metal. In the outer coordination sphere, sometimes referred to as
the second sphere, other ions are attached to the complex ion. The following table is a
summary of Werner's observations:

Initial compound Resulting compounds upon adding AgNO3

CoCl3·6NH3 [Co(NH3)6]3+(Cl-)3

CoCl3·5NH3 [Co(NH3)5Cl]2+(Cl-)2

CoCl3·4NH3 [Co(NH3)4Cl2]+(Cl-)

CoCl3·3NH3 [Co(NH3)3Cl3]

As the table above shows, the complex ion [Co(NH3)6]3+ is countered by the three chloride ions.
The multi-level binding of coordination complexes plays an important role in determining the
dissociation of these complexes in aqueous solution. For
example, [Co(NH3)5Cl]Cl2[Co(NH3)5Cl]Cl2 dissociates into three ions
while [Co(NH3)4Cl2]Cl[Co(NH3)4Cl2]Cl dissociates into two ions. By applying a current through the
aqueous solutions of the resulting complex compounds, Werner measured the electrical
conductivity and thus the dissociation properties of the complex compounds. The results
confirmed his hypothesis of the formation of complex compounds. It is important to note that
the above compounds have a coordination number of 6, which is a common coordination

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number for many inorganic complexes. Coordination numbers for complex compounds typically
range from 1 to 16.
DEFINITION
Coordination compounds are chemical compounds that consist of an array of anions or neutral
molecules that are bound to a central atom via coordinate covalent bonds. Coordination
compounds are also referred to as coordination complexes. These molecules or ions that are
bound to the central atom are referred to as ligands (also known as complexing agents).
Coordination compounds are also defined as compounds in which a central metal atom or ion is
linked to a number of ions or neutral molecules by coordinate bonds or which contain complex
ions. Examples- K4[Fe(CN)6]; [ Cu(NH3)4]SO4; Ni(CO)4.
Coordination compounds can also be defined as one in which the central metal or ion is
attached to molecules. Ions or atoms in number exceeding the charge or oxidation number of
atom or ion e.g [Co(NH3)6]Cl3
Many coordination compounds contain a metallic element as the central atom and are
therefore referred to as metal complexes. These types of coordination complexes generally
consist of a transition element as the central atom. The central atom in these complexes is
called the coordination centre.
TERMS
A complex ion is an electrically charged radical which is formed by the union of a metal cation
with one or more neutral molecules or anions e.g [PtCl6]2-, [Co(NH3)6]
Coordination Entity
A chemical compound in which the central ion or atom (or the coordination centre) is bound to
a set number of atoms, molecules, or ions is called a coordination entity.
Some examples of such coordination entities include [CoCl 3(NH3)3], and [Fe(CN)6]4-

Central Atoms and Central Ions

The atoms and ions to which a set number of atoms, molecules, or ions are bound are referred
to as the central atoms and the central ions.
In coordination compounds, the central atoms or ions are typically Lewis Acids and can,
therefore, act as electron-pair acceptors.

Ligands
The atoms, molecules, or ions that are bound to the coordination centre or the central
atom/ion are referred to as ligands. Ligands generally act as donor partners i.e. donate one or
more pair of electrons to the central metal atom/ion. But in metallic carbonyl CO molecule acts
both as a donor and acceptor, M CO, ligands are arranged around the metal ion inside the

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first sphere of attraction in preferred geometry which may be linear, tetrahedral, square planar
octahedral etc.
Ligands can either be simple ions or molecules (such as Cl– or NH 3) or in the form of relatively
large molecules, such as ethane-1,2-diamine (NH 2-CH2-CH2-NH2).

Coordination Number/ligancy
The coordination number of the central atom in the coordination compound refers to the total
number of sigma bonds through which the ligands are bound to the coordination centre.
It can also be defined as the total number of donor atoms (coordinating atoms) directly
attached to the central atom/ ion. It represents the total number of chemical bonds formed
between the central metal ion and the donor atoms of the ligands. For example, in the
coordination complex given by [Ni(NH3)4]2+, the coordination number of nickel is 4, In [Fe(CN)6]3-
the CN is 6
Coordination Sphere
This is the non-ionizable part of a complex compound consisting of a central transition metal
ion surrounded by neighbouring atoms or groups enclosed in square brackets.
The coordination centre, the ligands attached to the coordination centre, and the net charge of
the chemical compound as a whole, form the coordination sphere when written together. This
coordination sphere is usually accompanied by a counter ion (the ionizable groups that attach
to charged coordination complexes).
Example: [Co(NH3)6]Cl3 – coordination sphere

Coordination Polyhedron
The geometric shape formed by the attachment of the ligands to the coordination centre is
called the coordination polyhedron.
Examples of such spatial arrangements in coordination compounds include tetrahedral,
octahedral and square planar.

Oxidation Number
The oxidation number of the central atom can be calculated by finding the charge associated
with it when all the electron pairs that are donated by the ligands are removed from it.
For example, the oxidation number of the platinum atom in the complex [PtCl6]2- is +4.

Homoleptic and Heteroleptic Complex

 When the coordination centre is bound to only one type of electron pair donating ligand
group, the coordination complex is called a homoleptic complex, for example
[Cu(CN)4]3-.

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  When the central atom is bound to many different types of ligands, the coordination
compound in question is called a heteroleptic complex, an example of which is
[Co(NH3)4Cl2]+.

Properties of Coordination Compounds

The general properties of coordination compounds are:

 The coordination compounds formed by the transition elements are coloured due to the
presence of unpaired electrons that absorb light in their electronic transitions. For
example, the complexes containing Iron(II) can exhibit green and pale green colours, but
the coordination compounds containing iron(III) have a brown or yellowish-brown
colour.
 When the coordination centre is a metal, the corresponding coordination complexes
have a magnetic nature due to the presence of unpaired electrons.
 Coordination compounds exhibit a variety of chemical reactivity. They can be a part of
inner-sphere electron transfer reactions as well as outer-sphere electron transfers.
 Complex compounds with certain ligands have the ability to aid in the transformation of
molecules in a catalytic or stoichiometric manner.

Double Salts and Coordination Complex

Double Salts
Double salts are completely ionizable in aqueous solutions and each ion in the solution gives
the corresponding confirmatory test.
Example: Potash Alum is double sulphate. It is K2SO4.Al2(SO4)3.24H2O on Ionization it gives:
K+, SO2−4 and Al+3 ions which response to the corresponding tests.

Coordination Complex
Co-ordinate complexes are incompletely ionizable in the aqueous solutions. These give a
complex ion which does not show complete ionization.
Example: Potassium Ferrocyanide. [K4Fe(CN)6] It ionizes to give K+ and [Fe(CN)6]−4 [ferro cyanide
ions]

Types of Coordination Complexes

 Cationic complexes: In this co-ordination sphere is a cation. Example: [Co(NH 3)6]Cl3

 Anionic complexes: In this co-ordination sphere is Anion. Example: K4[Fe(CN)6]
 Neutral Complexes: In this co-ordination sphere is neither cation nor anion. Example:
[Ni(CO)4]

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  Homoleptic complex: The complex consists of a similar type of ligands. Example:
K4[Fe(CN)6]
 Heteroleptic complexes: These consist of different types of ligands. Example:
[Co(NH3)5Cl]SO4
 Mononuclear complexes: In this coordination sphere has a single transition metal ion.
Example: K4[Fe(CN)6]
 Polynuclear complexes: More than one transition metal ion is present. Example:

Nomenclature of Coordination Compounds

Rules for Naming Coordination Compounds:

The standard rules that must be followed in the nomenclature of coordination compounds are
described below.

1. The ligands are always written before the central metal ion in the naming of complex
coordination complexes.
2. When the coordination centre is bound to more than one ligand, the names of the
ligands are written in an alphabetical order which is not affected by the numerical
prefixes that must be applied to the ligands.
3. When there are many monodentate ligands present in the coordination compound, the
prefixes that give insight into the number of ligands are of the type: di-, tri-, tetra-, and
so on.
4. When there are many polydentate ligands attached to the central metal ion, the
prefixes are of the form bis-, tris-, and so on.
5. The names of the anions present in a coordination compound must end with the letter
‘o’, which generally replaces the letter ‘e’. Therefore, the sulfate anion must be written
as ‘sulfato’ and the chloride anion must be written as ‘chlorido’.
6. The following neutral ligands are assigned specific names in coordination compounds:
NH3 (ammine), H2O (aqua or aquo), CO (carbonyl), NO (nitrosyl).
7. After the ligands are named, the name of the central metal atom is written. If the
complex has an anionic charge associated with it, the suffix ‘-ate’ is applied.
8. When writing the name of the central metallic atom in an anionic complex, priority is
given to the Latin name of the metal if it exists (with the exception of mercury).
9. The oxidation state of the central metal atom/ion must be specified with the help of
roman numerals that are enclosed in a set of parentheses.
10. If the coordination compound is accompanied by a counter ion, the cationic entity must
be written before the anionic entity.

Some examples:

 K4[Fe(CN)6]: Potassium hexa cyanide ferrate (II)

 [Ni(CN)4]−2: Tetra cyano Nickelate (II) ion.

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  [Zn(OH)4]−2: Tetra hydroxide zincate (II) ion.
 [Ni(CO)4]: Tetra carbonyl Nickel (O).

What are Ligands in Coordination Compounds?

The surrounding atoms, ion and molecule around the central transition metal ion are known as
Ligands. They act as Lewis base and donate electron pairs to transition metal ion thus a dative
bond is formed between ligands and the transition metal ion. Hence these compounds are
coordination complexes.

Types of Ligands
Based on the nature of the bond between the ligand and the central atom, ligands are classified
as follows:

 Anionic ligands: CN–, Br–, Cl–

 Cationic ligands: NO+
 Neutral ligands: CO, H2O, NH3
Ligands can be further classified as:

Unidentate Ligands
The ligands which only have one atom that can bind to the coordination centre are called
unidentate ligands. Ammonia (NH3) is a great example of a unidentate ligand. Some common
unidentate are Cl–, H2O etc.

Bidentate Ligands
Ligands which have the ability to bind to the central atom via two separate donor atoms, such
as ethane-1,2-diamine, are referred to as bidentate ligands. Oxalate ion is a bidentate as it can
bond through two atoms to the central atom in a coordination compound and Ethane-1, 2-
diamine:

Polydentate Ligands
Some ligands have many donor atoms that can bind to the coordination centre. These ligands
are often referred to as polydentate ligands.
A great example of a polydentate ligand is the EDTA4- ion (ethylene diamine tetraacetate ion),
which can bind to the coordination centre via its four oxygen atoms and two nitrogen atoms.

Chelate Ligand
When a polydentate ligand attaches itself to the same central metal atom through two or more
donor atoms, it is known as a chelate ligand. The atoms that ligate to the metal ion are termed
as the denticity of such ligands.

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 Ambidentate Ligand
Some ligands have the ability to bind to the central atom via the atoms of two different
elements.
For example, the SCN– ion can bind to a ligand via the nitrogen atom or via the sulfur atom.
Such ligands are known as ambidentate ligands.
Steps for identifying the coordination number of a coordination compound:
1. Identify the central atom in the chemical formula. ...
2. Locate the atom, molecule, or ion nearest the central metal atom. ...
3. Add the number of atoms of the nearest atom/molecule/ions. ...
4. Find the total number of nearest atoms.

Werner’s Theory
Alfred Werner in 1898 proposed Werner’s theory explaining the structure of coordination
compounds.
Werner’s Experiment: By mixing AgNO3 (silver nitrate) with CoCl3·6NH3, all three chloride ions
got converted to AgCl (silver chloride). However, when AgNO3 was mixed with CoCl 3·5NH3, two
moles of AgCl were formed.
Further, on mixing CoCl3·4NH3 with AgNO3, one mole of AgCl was formed. Based on this
observation, the following Werner’s theory was postulated:

Postulates of Werner’s Theory

 The central metal atom in the coordination compound exhibits two types of valency,
namely, primary and secondary linkages or valencies.
 Primary linkages are ionizable and are satisfied by the negative ions.
 Secondary linkages are non-ionizable. These are satisfied by negative ions. Also, the
secondary valence is fixed for any metal and is equal to its coordination number.
 The ions bounded by the secondary linkages to the metal exhibit characteristic spatial
arrangements corresponding to different coordination numbers.

Difference between Primary and Secondary Valency in Coordination Compounds

Werner’s Theory

Primary valency Secondary valency

These are ionizable These are Non-ionizable

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 Satisfied by charged ions Satisfied by ligands

Primary valency does not help in the structure Secondary valency helps in

of complex structure

It can also function as a secondary valence It cannot function as a primary

valency

Limitations of Werner’s Theory

1. It fails to explain the magnetic, colour and optical properties shown by coordination
compounds.
2. It failed to explain the reason why all elements don’t form coordination compounds.
3. It failed to explain the directional properties of bonds in coordination compounds.
4. This theory does not explain the stability of the complex
5. This theory could not explain the nature of complexes

Effective Atomic Number Rule

Effective Atomic Number Rule is proposed by Sidgwick. The total number of electrons passed by
central transition metal ion after the donation of electrons by the ligand an effective atomic
number.
A complex is stable if the effective atomic number is equal to the atomic number of nearest
inert gas.
Example: Calculate the effective atomic number of the following complexes:

 K4[Fe(CN)6]
 [Co(NH3)]Cl3
1. K4[Fe(CN)6]
Number of electrons in Fe2+ = 24
Number of electrons by Six CN = 2×6 = 12
Total number of electrons possessed by Fe2+ = 24 + 12
Therefore, the effective atomic number = 36.
2. [Co(NH3)]Cl3

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Number of electrons in Co+3 = 24
Number of electrons by Six NH3 = 2×6 = 12
Total number of electrons possessed by Co+3 = 24 + 12
Therefore, the effective atomic number = 36.

Magnetic Properties of Complexes

1. The complex in which central transition metal ion has unpaired electrons
is Paramagnetic.
2. The complex in which central transition metal ion has no unpaired electrons is
diamagnetic.
3. The magnetic moment of a complex is calculated by the spin only formula

M = √[n(n+2)] BM
BM = Bohr Magneton
The magnetic moment of complex compounds depends upon:

 Type of hybridization.
 The oxidation state of central transition metal ion.
 The number of unpaired electrons.

Colour of Complexes
Complexes in which central transition metal ion contains unpaired electrons shows colour. It is
‘d – d’ transition. The colour of complexes depends upon:

 Number of unpaired electrons in transition metal ion

 Nature of ligands
 The oxidation state of central transition metal ion
 The wavelength of light absorbed and emitted
 The proportion of ligands in the coordination sphere
Example: [Ni(H2O)6]+2+en(aq)→[Ni(H2O)4en] +2 – Green Pale blue

Bonding in Metal Complexes [Metal Carbonyls]

Complexes in which carbon monoxide acts as ligands are metal carbonyls

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Example:  [Ni(CO)4] Tetracarbonyl Nickel (0) and [Fe(CO) 5] Penta Carbonyl Iron (0) In these
complexes, complexes, a′σ‘ bond is formed by the overlapping of vacant ‘d’ orbital of metal ion
and filled orbital of C-atom (carbon).
A π bond is formed by the lateral overlapping of filled inner orbitals of metal ion and vacant of
the carbon atom. Thus synergic bonding exist in metal carbonyls

Applications of Coordination Compounds

The characteristic properties possessed by coordination compounds that were discussed in the
previous subsection make them extremely useful in various processes and industries. A major
application of coordination compounds is their use as catalysts, which serve to alter the rate of
chemical reactions. Certain complex metal catalysts, for example, play a key role in the
production of polyethylene and polypropylene.
Some of these applications of coordination compounds can be found below:

 The colour of the coordination compounds containing transition metals causes them to
be extensively used in industries for the colouration of materials. They find applications
in the dye and pigment industries.
 Some complex compounds containing cyanide as a ligand are used in the process of
electroplating. These compounds are also very useful in photography.
 Coordination complexes are very useful in the extraction of many metals from their
ores. For example, nickel and cobalt can be extracted from their ores via hydro-
metallurgical processes involving ions of coordination compounds.

Applications in Biology/ living systems

 Haemoglobin consists of Haeme complex-ion which has tetrapyrrole Porphyrin ring

structure with central Fe2+ ion.
 Vitamin B12 consists of tetrapyrrole porphyrin ring complex with central Co +3 ion and its
coordination number is 6.
 Photosynthesis is made possible in green plant due to the presence
of Magnesium complex chlorophyll used to trap the required light energy .

Applications In Laboratory

 Ni+2 is estimated using a complexing agent Dimethylglyoxime (DMG).

The hardness of water is estimated using complexes of Ca++, Mg++ with EDTA
In Medicine: Cisplatin is used in the treatment of cancer.
The chelating ligand EDTA is used in treatment of lead poisoning.
Technetium complexes are used in imaging of internal organ in living organisms.
Auranofin (gold complex) is used in treatment of arthritis. Budotitane and titanocene dichloride
(anticancer drugs) are titanium complexes.

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 In Photography: Developing of the film involves complex formation.
 In Metallurgy: In the extraction of gold, silver by Mac Arthur Forest Process involves a
complex of cyanide ions. The purification of nickel by converting the metal to the
gaseous compound Ni(CO)4

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