Transition Metals

Two terms d-block metal and transition metal are often used
interchangeably; however, they do not mean the same thing. The IUPAC
definition of a transition metal is that it is an element that has incomplete
d sub-shell in either the neutral atom or its ion. Thus the group 12
elements (Zn, Cd and Hg) are members of the d-block but are not
transition elements. To make the study of the d-block element easier, we
will treat each row separately and each row will be refers to as a series,
with the 3d series the first row of the block (period 4).
The table below gives the name, chemical symbol, atomic number and
electronic configuration of the first row transition elements.
S/ Name Symbo Atomic Electronic M.P Metallic
No. l Number Configuration (oC) Radius
1. Scandium Sc 21 [Ar]4s23d1 1814 164
2. Titanium Ti 22 [Ar]4s23d2 1941 147
3. Vanadium V 23 [Ar]4s23d3 2183 135
4. Chromium Cr 24 [Ar]4s13d5 2180 129
5. Manganese Mn 25 [Ar]4s23d5 1519 137
6. Iron Fe 26 [Ar]4s23d6 1811 126
7. Cobalt Co 27 [Ar]4s23d7 1768 125
8. Nickel Ni 28 [Ar]4s23d8 1728 125
9. Copper Cu 29 [Ar]4s13d10 1358 128
10. Zinc Zn 30 [Ar]4s23d10 693 137

Electron Configurations of the Transition Metals and Their Ions

Periods 4 through 7. Each series represents the filling of five d-orbitals
and, thus, contains ten elements, for a total of 40 transition elements.
The first of these series occurs in Period 4 and consists of scandium (Sc)
through zinc (Zn) (Table 1).

Two points are important to be considered:

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 1. Electron configurations of the atoms. Despite several
exceptions, in general, the
Condensed ground-state electron configuration for the atoms in each d-
block series is
[Noble gas] ns2 (n - 1)dx , with n = 4 to 7 and x = 1 to 10
In Periods 6 and 7, the condensed configuration includes the f - sublevel:
[Noble gas] ns2(n-2)f14(n - 1)dx, with n = 6 or 7
The partial (valence-level) electron configuration for the d-block elements
excludes the noble gas core and the filled inner f - sublevel: ns 2(n - 1)dx
2. Electron configurations of the ions. Transition metal ions are
formed through the loss of ns electrons before (n - 1)d electrons. Thus,
the electron configuration of Ti 2+ is [Ar]3d2, not [Ar] 4s2, and Ti2+ is
referred to as a d2 ion. Ions of different metals with the same
configuration often have similar properties: for example, both
Mn2+ and Fe3+ (d5 ions) have pale colors in solution and form
complex ions with similar magnetic properties.
Worked Example: Write condensed electron configurations for the
following:
(a) Zr (b) V3+ (c) Mo3+
. (Assume that elements in higher periods behave like those in Period 4.)
Solution
We locate the element in the periodic table and count its position in the
respective transition series. These elements are in Periods 4 and 5, so the
general configuration is [noble gas] ns 2(n - 1)dx. For the ions, we recall
that ns electrons are lost first.
(a) Zr is the second element in the 4d series: [Kr] 5s 24d2.
(b) V is the third element in the 3d series: [Ar] 4s 23d3. In forming V3+,
three electrons are lost (two 4sand one 3d), so V 3+ is a d2 ion: [Ar] 3d2.
(c) Mo lies below Cr in Group 6. Remember that Cr has a configuration
with half-filled 4s and 3d orbitals, so we expect the same pattern for Mo.
Thus, Mo is [Kr] 5s14d5. To form the ion, Mo loses the one 5sand two of
the 4delectrons, so Mo3+ is a d3 ion: [Kr] 4d3

Exercise 1:

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Write partial electron configurations (no noble-gas core or filled inner
sublevels) for the following:
a) Ti4+ b) Cr2+ c) Fe3+ d) Cu+
UNIQUE PROPERTIES OF TRANSITION ELEMENTS
Color
Most main-group ionic compounds are colorless because the metal ion
has a filled outer level (noble gas electron configuration). In contrast,
electrons in a partially filled d sublevel can absorb visible wavelengths
and move to slightly higher energy d orbitals. As a result, many transition
metal compounds have striking colors. Exceptions are the compounds of
scandium, titanium (IV), and zinc, which are colorless because their metal
ions have either an empty d sublevel (Sc3+ or Ti4+: [Ar] 3d0) or a filled one
(Zn2+: [Ar] 3d10)
Magnetism
Magnetic properties are also related to sublevel occupancy. A
paramagnetic substance has atoms or ions with unpaired electrons, which
cause it to be attracted to an external magnetic field. A diamagnetic
substance has only paired electrons, so it is unaffected (or slightly
repelled) by a magnetic field. Most main-group metal ions are
diamagnetic for the same reason they are colorless: all their electrons are
paired. In contrast, many transition metal compounds are paramagnetic
because of their unpaired d electrons. For example, MnSO4 is
paramagnetic, but CaSO4 is diamagnetic. The Ca2+ ion has the electron
configuration of argon, whereas Mn2+ has a d5 configuration. Transition
metal ions with a d0 or d10 configuration are diamagnetic and colorless.
Variable oxidation state
The common oxidation states for each element include +2, +3, or both.
The +3 oxidation states are more stable at the beginning of the series,
whereas toward the end, the +2 oxidation states are more stable. The
reason is that the ionization energies increase gradually from left to right.
However, the third ionization energy (when an electron is removed from
the 3d orbital) increases more sharply than the first and second ionization
energies. Because it takes more energy to remove the third electron from
the metals near the end of the row than from those near the beginning,
the metals near the end tend to form M2+ ions rather than M3+ ions.
The highest oxidation state is +7, for manganese (4s23d5). Transition
metals usually exhibit their highest oxidation states in compounds with
very electronegative elements such as oxygen and fluorine —for
example, VF5, CrO3, and Mn2O7.

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Catalytic ability
Many transition metals such as Ni and Pt are good heterogeneous catalyst
due to their ability to adsorb gaseous species. The possibility of multiple
oxidation state seems to account for the ability of some transition metal
ions to serves as catalysts in many oxidation reduction reactions. In other
type of catalysis, formation of complex ion may play an important role.
Catalysis is an essential aspect of about 90% of all chemical
manufacturing processes, and transition metals are often the key
elements of the catalysts used. To mention but a few examples, Nickel is
used in the hydrogenation of oils; Pt, Pd and Rh are used in catalytic
converters in automobile. Other examples include Fe 3O4 which is the main
component of the catalyst used in the synthesis of ammonia and V 2O5 is
used in the conversion of SO2 to SO3 in the manufacture of sulphuric acid.
Coordination Compounds
The most distinctive aspect of transition metal chemistry is the formation
of coordination compounds (also called complexes). These are
substances that contain at least one complex ion, a species consisting
of a central metal cation (either a transition metal or a main-group metal)
that is bonded to molecules and/or anions called ligands. In order to
maintain charge neutrality in the coordination compound, the complex
ion is typically associated with other ions, called counter ions.
A typical example of coordination compound is [Co(NH 3)6]Cl3, the complex
ion (always enclosed in square brackets) is [Co(NH 3)6]3+, the six NH3
molecules bonded to the central Co 3+ are ligands, and the three Cl - ions
are counter ions. A coordination compound behaves like an electrolyte in
water: the complex ion and counter ions separate from each other. But
the complex ion behaves like a polyatomic ion: the ligands and central
metal ion remain attached. Thus, 1 mol of [Co(NH 3)6]Cl3 yields 1 mol of
[Co(NH3)6]3+ ions and 3 mol of Cl- ions.

ELECTRONIC STRUCTURE AND SPECTRA OF TRANSITION METAL

COMPLEXES
There are three theories that try to explain the bonding and properties of
transition metal complexes. They are
 The valence bond theory, VBT
 The crystal field theory, CFT and
 The molecular orbital theory MO.
Valence bond theory

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This theory was developed by Pauling. The central idea of this theory is
that coordination compounds contain complex ions, in which the ligands
formed coordinate bonds to the central metal ion. Thus the ligands must
have a lone pair of electrons and the metal must have an empty orbital of
suitable energy available for bonding. The theory predicted the shape and
stability of the complex from the atomic orbitals on the metal that are
used for bonding.
To understand the valence bond theory better, let us consider the
formation of Co3+ complex. The outer electronic configuration of Co atom
is 3d74s2. The Co3+ ion will have 3d6 structure and the electrons will be
arranged as in figure 1.
3d 4s 4p 4d

Fig 1: Arrangement of electrons in Co3+ ions

Six empty orbital are required for this metal ion to form a complex with
six ligands. The orbitals used are the 4s, three 4p and two 4d. These are
hybridized to give a set of six equivalent orbitals i.e sp 3d2 hybrid orbitals.
A ligand orbital containing a lone pair of electrons overlap with an empty
hybrid orbital on the metal ion. In this way a σ-bond is formed with each
ligand. The d-orbitals used are the d x −d y and d z . Electron pairs from the
2 2 2

ligands are shown as

3d 4d

(sp3d2 hybridization) Unhybridized d-orbitals

Fig 2: Arrangement of electrons in Co (III) complex

To minimize repulsion between the electrons, the complex adopts
octahedral shape and it is a high spin or outer orbital complex as it
involves the use of 4d orbitals. The energy of these orbitals is quite high,
so the complex will be reactive or labile. The magnetic moment depends
on the number of unpaired electrons. As we can see, the 3d level contain
the maximum number of unpaired electrons for a d 6 arrangement, so this
is some time called a high spin or spin free complex.

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Another possible arrangement of electrons in a metal ion with d 6 structure
is as shown in the diagram below. As before, the lone pairs from the
ligands are shown as
3d 4s 4p 4d

(d2sp3 hybridization)

Figure 3: Arrangement of electrons in low spin Co(III) octahedral

complex
This arrangement gives rise to octahedral low-spin inner orbital complex.
This is because low energy inner d-orbitals are used. Such complexes are
more stable than the outer orbital complex. The unpaired electrons have
been forced to paired-up and so this is now a low spin complex and thus
diamagnetic.
Tetrahedral and square planar complexes
The metal ion could also form four coordinate complexes, and two
different arrangements are possible.
3d 4s 4p

(sp3 hybridization)

Figure 4: Arrangement of electrons for d6 metal ion in tetrahedral

complex

This arrangement makes the complex to adopt tetrahedral shape. The

other possible arrangement is given as below
3d 4s 4p

6
 (dsp3 hybridization)
Square planar shape

Figure 5: Arrangement of electrons for d 6 metal ion in square

planar complex
Success of the valence bond theory
The valence bond theory is successful in explaining the magnetic
properties and the shape of transition metal complexes.
Failure of Valence Bond Theory
Despite the successes of the valence bond theory, it still suffer the
following set back
1. The theory can say nothing about the colour and electronic
spectroscopic properties or about the kinetic inertness that is a
characteristic of the low-spin d6 configuration.
2. The model implies a distinction between high- and low-spin complexes
that is actually misleading.
3. It does not explain why magnetic properties change with temperature.
4. Finally, it cannot tell us why certain ligands are associated with the
formation of high- (or low-) spin complexes.
For these reasons, it has largely been superseded by the crystal field
theory.

CRYSTAL FIELD THEORY (CFT)

In the crystal field theory, bonding in a complex ion is considered to be
an electrostatic attraction between the positively charged nucleus of the
central metal ion and electrons in the ligands. Repulsions also occur
between the electrons in the ligand and electrons in the central ion. The
theory focuses on these repulsions which causes the d-orbitals to split
into two groups of different energies, as shown in figure 6 below

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Figure 6: Splitting of d energy levels in the formation of an octahedral complex ion. The d-
orbital energy levels of the free central ion are raised in the presence of ligands to the
average level shown, but the five levels are split into two groups.
When ligands approach degenerate d-orbitals in the central ion their
energies are raised. However the energies of these orbital are not raised
to the same extent. Two out of these five d-orbitals ( d x d ¿ or d z ) have their 2−¿
y2
2

energies raised with respect to the average d-orbital for a central metal
ion in the field of the ligands. The energies of the remaining three d-
orbital (d xy ,d xz ∧d yz) are lowered with respect to the average d-orbital
energy. The difference in energy between the two groups of d orbitals is
called crystal field splitting and is represented by the symbol Δ o as shown
in Figure 6.
The removal of the degeneracy of the d orbitals by the crystal field has
important consequences for the electron configurations of transition
metal ions having between 4 and 7 electrons in the d orbital. Consider the
transition metal ion Cr2+ with a d4 configuration. If the four d electrons are
assigned to the orbitals of lowest energy first, the first three electrons go
into thed xy ,d xz ∧d yz orbitals according to Hand’s rule but what about the
fourth electron? The fourth electron must either paired up with any one of
the electrons in the d xy ,d xz ∧d yz, or go into either d x d ¿ or d z .
2−¿
y2
2

Fig. 7a: low-spin arrangement of electron in d4 ion Fig. 7b: arrangement of electron in high spin d4 ion

Where the fourth electron goes depends on the magnitudes of two

opposing energies i.e the pairing energy (P), (the energy required to
force an electron into an orbital that is already occupied by an electron)
and the crystal field splitting energy, Δo, (CFSE). If Δo > P, greater stability
is obtained if the fourth electron is paired with one in the lower level. On
the other hand, If Δo < P, greater stability is obtained by keeping the
electrons unpaired. Thus, for octahedral chromium (II) complexes, there
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are two possibilities with different number of unpaired electrons. In one
case, there are four unpaired electrons when Δ o < P this situation
corresponds to the maximum number of unpaired electrons and is
referred to as high spin. Ligands such as H2O and F- and other halides
produce only a small crystal field splitting, leading to high-spin
complexes; such ligands are said to be weak-field ligands. An example
high-spin complex is [Cr(H2O)6]3+ in which the H2O acts as a weak-field
ligand. In the other case, when ∆ ° > P ; there are only two unpaired
electrons and this corresponds to the minimum number of unpaired
electrons possible. This is referred to as low- spin complex. A good
example of this type is hexacyanoferrate (III), [Fe(CN) 6]3−. Ligands, such
as NH3and CN− which lead to the formation of this type of complexes rare
referred to as strong field ligans.
produce large crystal field splitting, leading to low-spin complexes; such
[Cr(NH3)6]3+ ligands are said to be strong-field ligands. Is a strong-field
complex.

The value of this splitting (Δo) depends the position of the ligand on
the spectrochemical series and varies with the identity and charge on the
metal atom. The separation of the two set of orbitals is called the ligand-
field splitting parameter, Δo, Here the subscript o denotes an octahedral
crystal field. The energy level that corresponds to the spherical
symmetric environment defines the barycentre of the array of levels, with
the eg orbitals lying at 3/5Δo above the barycenter and the 3 t 2g orbitals
lying 2/5Δo below it. In the representation of the electronic configuration
of atoms, a subscript is used to indicate the number of electrons in each
set.

FACTORS AFFECTING Δo

The following are the factors affecting the value of the ligand-field
splitting parameter

i. Nature of the ligand

ii. Identity of the central metal ion
iii. Charge on the central metal ion
iv. Location of the central metal in the periodic table

Nature of the ligand: The ligand field splitting parameter (LFSP) Δo

varies systematically with the identity of the ligand. For instance in the of
complexes [Cox(NH3)5]n+ with x= I-, Cl-, Br-, H2O and NH3, the colour
changes from purple (for x=I-) through pink (for x= Cl-) to yellow with x=
NH3. This shows that the energy of the lowest electronic transition (and
therefore Δo) increase as the ligands are varied along the series. The
same order is followed regardless of the identity of the metal. On the
basis of these observations Ryutaro Tsuchida proposed that ligands could
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be arranged in a spectrochemical series, in which members are arranged
in order of transition that occur when these ligands are present in a
complex.

I-< Br- < S2- < SCN- < Cl- < NO2 < N3- < F- < OH- < C2O42- < H2O < NCS- <
CH3CN < Py < NH3 < en < bipy < Phen < NO2 < PPh3 < CN- < CO

A ligand that gives rise to a high energy transition such as CO is referred

to as strong-field ligand, whereas one that gives rise to a low-energy
transition such as Br- is referred to as weak-field liagand.

Identity of the central metal ion: ligand field strength also depends
on the nature of the central metal ion, the order being approximately

Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mo3+ < Rh3+ < Ru3+ <
Pd4+ < Ir3+ < Pt4+

It is evident from the above series that the value of Δ o increases with
increasing oxidation state of the central metal ion (compare the two
entries for Fe and Co). The value of Δ o also increases down a group
(compare, for instance, the locations of Co, Rh, and Ir). The variation with
oxidation state reflects the smaller size of more highly charged ions and
the consequently shorter metal-ligand distances and stronger interaction
energies. The increase down a group reflects the larger size of the 4d and
5d orbitals compared with the compact 3d orbitals and the consequent
stronger interactions with the ligands.
Weak field ligand Strong field ligand
Configuratio No. of unpaired Configuratio No. of
n electrons n unpaired
electrons
3d4 t2g3eg1 4 t2g4 2
3d5 t2g3eg2 5 t2g5 1
3d6 t2g4eg2 4 t2g6 0
3d7 t2g5eg2 3 t2g6eg1 1

The crystal field theory is based on purely electrostatic attraction. At

first sight this seems to be a most improbable assumption. Nevertheless,
the theory is remarkably successful in explaining the shapes of
complexes, their spectra and their magnetic properties. Calculations can
be carried out quite simply. The disadvantage of the theory is that it

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ignores evidence that some covalent bonding does occur in at least some
transition metal complexes:

1. Compounds in the zero oxidation state such as nickel carbonyl

[Ni0(CO)4] have no electrostatic attraction between the metal and the
ligands. Thus the bonding must be covalent.
2. The order of ligands in the spectrochemical series cannot be explained
solely on electrostatic grounds.
3. There is some evidence from nuclear magnetic resonance and electron
spin resonance that there is some unpaired electron density on the
ligands. This suggests the sharing of electrons, and hence some
covalency.

These short comings of the crystal field theory call for another theory to
explain the existence of complexes such as [Ni 0(CO)4], order of ligands in
the spectrochemical series and covalency in some complexes.

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