Chemistry of Transition Metals and their compounds

There are about 50 transition elements and they have interesting chemical properties
such as a variety of different oxidation states in their compounds, their extensive
ability to form complexes, useful and often colourful compounds.

We shall only consider the first row transition elements.

A transition element is a d-block element that forms some compounds containing its
ion with an incomplete d-subshell.

Strictly speaking, Sc and Zn are not considered to be transition elements.

You have to know the electronic configurations of the elements and their ions by
looking at the periodic table.

The 3d block contains ten elements, because the 3d subshell contains five orbitals,
each can accommodate 2 electrons of opposite spins. All these elements involve the
filling of the 3d set of orbitals.

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The 4s orbital is lower in energy than 3d. 4s orbital is filled before 3d orbital.

However, exceptions:
Cr [Ar] 3d5 4s1
Cu [Ar] 3d10 4s1
3d5 - half filled d orbital is preferred.
3d10 full d-orbital

Why? Symmetrical 3d cloud of electrons that screens the nucleus more effectively
than the other configurations.

Before electrons occupy 4s and 3d, 4s is energetically more stable than 3d.
When 3d orbitals are occupied by electrons, they repel the 4s electrons even further
from the nucleus and up to a higher energy level than the 3d orbitals.

Thus, the energy level of the 4s orbital is higher than that of the 3d orbitals.

Hence in forming ions, 4s electrons are removed before the 3d electrons.

Properties

Across transition elements: trend in atomic radii.

Decrease slightly/ remains relatively constant
Reasons : Nuclear charge increases Due to increase in number of protons
Electrons are added to the inner 3d subshell.
Screening effect increases.
Effective nuclear charge increases Slightly.

Across transition elements: trend in ionic radii

Decreases slightly/remains relatively constant
Reason: Electrons are removed from the outermost shell
Screening effect increases With increasing 3d electrons
Nuclear charge also increases.
Effective nuclear charge increases slightly.

Across main group elements Across transition elements

Trend in atomic Relatively invariant / decreases
Decreases significantly
radii slightly
Nuclear charge increases due
to
Nuclear charge increases due
increasing number of protons
to
Electrons are added to the 3d
increasing number of protons
subshell, which contributes to
Electrons are added to the
the
outermost shell
Reasons screening effect
Screening effect remains
Screening effect increases
constant
thereby
Effective nuclear charge
nullifying, to a considerable
increases
extent, the influence of each
significantly
additional proton in the nucleus
Effective nuclear charge

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 remains
almost constant (increases
slightly)

Trend in 1st I.E.

Increases only slightly
Reason : 1st IE involves removal of a 4s electron
Nuclear charge increases. Across the d-block, inc. In 3d electrons shield the effect of
increasing nuclear charge so that the 4s electron experiences only a small extra
attraction.
Energy required to remove the outermost electrons increases very slightly.

Trend in melting points and boiling points

Generally higher than s-block metals
Both 4s and 3d electrons are involved in metallic bonding
Mn has a relatively low mp and bp. Half-filled d-subshell, 3d electrons are less
available for delocalization. Weaker metallic bonding.
Fe to Zn, mp and bp generally decreases as electrons being to pair up in the 3d
orbitals. Less participation in metallic bonding.

Trend in densities : very high

Higher atomic masses
Small atomic radius, close packing of atoms, resulting in more no. Of atoms per unit
volume.
Sc to Cu, inc. In density

Electrical conductivity : Very good conductor of heat and electricity.

Can use 4s and inner 3d electrons for strong metallic bonding.

Chemical properties:

The transition metals and their compounds display chemical behaviour that differ from the
s-block metals and their compounds. The more important common features are:
s-block metals Transition metals
They can form ions and
They form ions and compounds compounds
with with the metal having a variety of
the metal having fixed oxidation oxidation states.
Oxidation states
states. Manganese: (+2) Mn , (+4)
2+

Group I metals: (+1) for all MnO2,

Group II metals: (+2) for all (+7) MnO4 .

Iron: (+2) Fe ; (+3) in Fe

2+ 3+

They and their compounds often

Catalytic properties
Formation of complex ions
They and their compounds
usually do
not show catalytic properties.
They do not readily form
complexes.
show
catalytic properties.
Iron, Fe, in the Haber process,
vanadium(V) oxide, V2O5, in the
Contact process.
FeSO4 or Fe2(SO4)3 in I/S2O82
reaction
They have a strong tendency to
form

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 complex ions.
[Cu(NH3)4]2+, [Fe(CN)6]3,
[Ag(NH3)2]+
They form coloured ions or
They form white solids or compounds.
Formation of coloured ions
colourless dichromate ion: orange,
or compounds
solutions. Iron(III) ion: yellow, MnO4:
purple

Oxidation states : can form often colored ions and compounds with the metal having
different oxidation states.

eg. manganese in its compounds can exhibit a range of oxidation numbers ranging
from +2 to +7.

The metals and their compounds often show catalytic properties.

eg. In the Contact Process (wiki this, this is out of syllabus but came out in exam
before), vanadium (V) oxide is used as a catalyst to convert sulfur dioxide into sulfur
trioxide.

They have a strong tendency to form complex ions.

They form often coloured ions or compounds.

Why do the various transition metal ions have variable oxidation states?

Reason : Close similarity in energy of the 4s and 3d electrons. Hence, once the 4s
electrons are removed, some or all of the 3d electrons may be removed without
requiring much more energy.

General trends in oxidation states:

In elemental states, elements assigned an oxidation number of zero.

No. Of available oxidation states of the elements increases from Sc to Mn.

There is a decrease in the no. of oxidation states exhibited by the elements Mn to
Zn. Pairing of d-electrons occurs.

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Diagram : Common oxidation states of the transition metal ions

Lower oxidation states are usually found in ionic compounds.

The higher oxidation states tend to involve covalency (eg. TiO2, V2O5, Mn2O7) and
oxo-anions (eg. MnO4-)

Redox reactions:

Generally, ions that have the transition metal in a high oxidation state tend to be
good oxidising agents.

Early transition metals in low oxidation states tend to be good reducing agents. Cr2+,
V2+.

Usually color change when transition metal ions undergo redox reactions.

You can use electrochemistry principles in determining E cell and predicting

whether a reaction is feasible. For example, potassium manganate(VII) oxidizes
iron(II) ions to iron(III) ions. The standard cell potential is greater than 0 volts and is
thermodynamically feasible.

Question : is there a redox reaction when V(NO3)2 reacts with KMnO4?

The reactions of the transition metals come under these categories:

Ligand exchange

One kind of ligand (discussed in the next section) is replaced by another.

For example, Cu(H2O)62+ + 4Cl- CuCl42- + 6H2O

Hydrolysis

One or more hydrogen ions is removed.

For example, Cu(H2O)62+(aq) + 2OH-(aq) Cu(H2O)4(OH)2(s) + 2H2O(l)

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 Redox

The oxidation state of the metal is changed by adding or removing one or more
electrons

For example, Co(NH3)62+ Co(NH3)63+ + e-

Transition Metals Part 2

Catalytic activity

Transition elements, both in the form of elements and in their compounds, are
important catalysts in organic synthesis and in chemical industries.

Definition : A catalyst is a substance that increases the rate of a reaction by

providing an alternative reaction pathway which has lower activation energy than the
uncatalysed reaction.

The catalyst takes part in the reaction but does not undergo any permanent chemical
change after the end of the reaction.

There are two types of catalysts:

Heterogeneous catalysts : they operate in a different physical state (phase) to the
reactants.
Homogeneous catalysts : they operate in the same phase as the reactants.

Heterogeneous catalysis:
Haber Process:
Equation :

Catalyst : finely divided iron

Firstly, gaseous reactant molecules, nitrogen and hydrogen gas molecules, diffuse
towards surface of iron catalyst.

The molecules adsorb onto surface of Fe catalyst.

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Fe 3d partially filled orbitals can accept electron pairs from reactant molecules.

The adsorption process bring reactant molecules closer together and in the correct
orientation.

NN and HH bonds are weakened.

Chemical reaction occurs, bonds break and new bonds form.

The catalysed pathway involves lower activation energy.

Faster reaction occurs.

After reaction, product molecules, ammonia molecules desorb and diffuse away from
catalyst surface so that active sites are exposed for further reaction.

Energy profile diagram:

Note:
Forward and reverse reactions are speeded up by catalyst. Products are not formed
more in quantity, but more quickly.
A catalyst provides a different mechanism for the reaction, with a new, lower
activation energy pathway.
A catalyst does not alter the enthalpy change of reaction.
Other catalysts: contact process, hydrogenation of vegetable oils to make margarine
by catalyst nickel.

Homogeneous catalysis:

The ability of transition metals to vary their oxidation state is the key factor in their
efficiency as homogeneous catalysts.
Iron(III) ions as catalyst.

Complex formation:
Transition elements can form complex compounds.

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High charge density of transition metal cations.

The cations have low lying vacant d orbitals that can be used to accommodate the
lone pair of electrons from the ligands, resulting in dative bond formation.

s-block cations : low polarizing power.

Complexes:

Transition metal cations, the water molecules involved in hydration are held to the
cation by stronger forces, leading to the formation of aqua Complexes general
formula [M(H2O)6]n+.
Ligands in complexes:
The ligands bind to the central metal ion by dative bonds.
L: --> Mn+

Examples of ligands: chloride ion, hydroxide ion, cyanide ion, water, ammonia,
carbon monoxide

Definition:
Ligands can be classified according to the number of dative bonds that it forms with
the central metal ion.

Mondentate ligand: Those that can form only one co-ordinate bond with a central
metal ion (or atom).

Polydentate ligand: Those that bond through electron pairs on more than one donor
atom.

Polydentate ligands are sometimes called chelating agents because of their ability to
hold a metal ion like a claw. (like a crab's claw holding onto its victim [the metal ion]
tightly)

Chelating ligands form stable complex ion with the central metal ion as the pincer-
like grip of these polydentate ligands are able to hold the cation more securely. Eg.
EDTA4-

EDTA ligand structure

The nucleophiles from organic chemistry and Lewis bases (electron pair donor)
from general inorganic chemistry fulfil the same role.

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Complexes :
A complex is formed by a central ion ( or atom) dative-bonded by surrounding ions or
molecules (known as ligands)
L --> M <-- L
A complex can be neutral, cationic or anionic.
In order to maintain charge neutrality in the compound, the complex ion is typically
associated with other ion, called counter ions.

Co-ordination number indicates the total number of dative bonds around the central
atom or ion. The most common values are 2, 4 and 6.
Silver diamine compounds. [Ag(NH3)2]+ ions (coordination number : 2) are used in
carbonyl chemistry to oxidise aldehydes to ions with the formation of a silver mirror
or a silver precipitate.

Points to consider when drawing the complex ions:

1. Oxidation state of central metal ion is to be written in Roman Numeral
(e.g. II, IV etc.)
2. Show plane using dotted lines
3. Dative covalent bonds to be indicated by the symbol
4. Lone pairs of electrons on ligands to be shown
5. Square bracket to be drawn and the overall charge to be indicated

IMPORTANT!
Why are transition metal complexes often coloured?

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Transition metal compounds are frequently coloured. This is due to the absorption of
light in the visible region of the electromagnetic spectrum.

Crystal field theory:

In a free transition metal atom, all five orbitals have the same energy.
As the ligands approach the metal ion, their electron pairs repel electrons in the five
d-orbital, causing all five d-orbitals increase in energy.
The ligands approach directly toward the lobes of the d x2 y2 and d z2 orbitals but
between the lobes of the dxy, dyz and dxz orbitals.

Energy of an electron in either the d x2 y2 and d z2 orbitals is higher because of

differe difference in delectrostatic repulsion. There is an energy gap between them.
- difference in energy.
Colours low wavelengths blue violet, green
High wavelength red, orange.
d-d transition : Jumping of an electron to an higher energy orbital.
For most transition metal complexes, the E corresponds to energy in the visible
energy region (400 to 700 nm) of spectrum.

Why are Zn2+ ions non-coloured?

Nature of ligands
Different ligands have different effects on the splitting of the d-orbitals. The larger the
splitting of energy levels, the shorter the wavelengths absorbed and the longer
wavelength light is thus observed.

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You need to know the Common transition metal compounds and their colours.
IMPORTANT!

The variety of color among transition metal complexes has long fascinated the
chemists.
For example, aqueous solutions of [Fe(H2O)6]3+ are red, [Co(H2O)6]2+ are pink,
[Ni(H2O)6]2+ are green, [Cu(H2O)6]2+ are blue and [Zn(H2O)6]2+
are colorless. Although the octahedral [Co(H2O)6]2+
are pink, those of tetrahedral [CoCl4]2- are blue. The green
color of [Ni(H2O)6]2+
turns blue when ammonia is added to give [Ni(NH3)6]2+.

Haemoglobin:
Haem binds with O2 molecule , O2 forms a dative bond with the iron to form a
species called oxyhaemoglobin.
CO ligand forms a very stable complex with hame
To form carboxyhaemoglobin which is very stable and displaces oxygen from the
cells of the body. Harmful effects on body are observed.

Review question:

Why do transition metal ions show a high tendency to form complexes?

Is the formation of a complex a reaction between a Lewis acid and a Lewis base?

Shapes of complexes: You can use VSEPR model to predict the shape of the
complexes (with limitations). Common shapes are linear, tetrahedral, square planar
and octahedral.

COMPLEMENTARY COLORS

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