CHEMISTRY OF D AND F BLOCK

ELEMENTS

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CHEM 421 COMPARATIVE STUDY OF d AND f BLOCK ELEMENTS (30 Lecture Hours, 30 Practical hours,
CF 3.0) PREREQUISITE CHEM 321

Purpose
The purpose of the course is to introduce the students to the concepts of organometallic Chemistry of d and f block elements with
emphasis on the basic principles and processes in the practical use of organometallic compounds as homogenous catalysts
employed in chemical industries.

Course objectives
At the end of the study the learners should be able to:-
 Describe physical and chemical properties of d and f block elements.
 Identify and explain characteristics of  acceptor or  acid ligands and their bonding modes.
 Describe molecular structures of metal carbonyls and nitrosyls.
 Describe the bonding in organometallic compounds of some d and f block elements
 Describe preparation of some organometallic compounds used in homogenous catalytic reactions.
 Identify and explain characteristics of  -extended ligands.

Course Description
General trends in physical and chemical properties along the period and down the group; organometallic compounds: Metal
carbonyls and other related compounds e.g. metal nitrosyls, cyancomplexes etc. Valence electron count (the 16 and 18 electron
rule): organometallic compounds of pi-extended ligand systems; organometallic catalytic reactions; spectral analysis and
characterization of organometallic compounds; metal-metal bonding and introduction to metal clusters.

Teaching methodologies
A combination of lectures, seminars, library search, case studies.

Instructional Materials
Textbooks, handouts, chalkboards, library services.

Methods of evaluation
Continuous assessment Tests 30%
 Class Tests 15%
 Assignments & Practicals 15%
End of semester examination 70%
Total 100%

Course Textbooks
1. Porterfield W.W. (1984) Inorganic Chemistry: A unified Approach. Addison – Wesley.
2. Cotton F. A. and Wilkinson G. (1988) Advanced Inorganic Chemistry. (5th Edition) Wiley – Interscience.
3. Collman J. P. and Hegedus L. S.: (1980) Principles and Applications of organometallic Chemistry. Mill Valley,
California University press.
4. Wilknson G., Stone F. G. A. and Abel E. W (1980) Comprehensive Organometallic Chemistry, Pergamon press
England.
5. Lukehart C. M. (1985) Fundamental Transition metal organometallic Chemistry. Pacific Groove California
Brooks/cole.
6. Purcell K. F. and Koltz J. C. (1977) Inorganic Chemistry, (International Edition), Saunders Philadelphia
7. Yamamoto A. (1986) Organtransition Metal Chemistry: Fundamental concepts and Applications. Wiley New
York.

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What is a transition metal?
The terms transition metal (or element) and d block element are sometimes used as if they mean the same
thing. They don't - there's a small difference between the two terms. Not all d block elements count as
transition metals.

A transition metal is one which forms one or more stable ions which have incompletely filled d orbitals.

On the basis of the definition outlined above, scandium, zinc and mercury don't count as transition metals -
even though they are members of the d block.

Scandium has the electronic structure [Ar] 3d14s2. When it forms ions, it always loses the 3 outer electrons
and ends up with an argon structure. The Sc3+ ion has no d electrons and so doesn't meet the definition.

Zinc has the electronic structure [Ar] 3d 104s2. When it forms ions, it always loses the two 4s electrons to give
a 2+ ion with the electronic structure [Ar] 3d10. The zinc ion has full d levels and doesn't meet the definition
either.

By contrast, copper, [Ar] 3d104s1, forms two ions. In the Cu+ ion the electronic structure is [Ar] 3d10.
However, the more common Cu2+ ion has the structure [Ar] 3d9. Copper is definitely a transition metal
because the Cu2+ ion has an incomplete d level.

The general electronic configuration of d-block elements is (n-1)d1-10ns1-2.

Properties of Transition Metals

1. Nearly all transition elements have typical metallic properties such as high tensile strength, ductility,
malleability, high thermal and electrical conductivity and metallic luster.
2. They have high melting and boiling points and have higher heats of vaporization than non-
transitional elements.
3. Transition elements have very high densities as compared to s block metals.
4. Most of them have colored compounds.
5. They have good tendencies to form complexes.
6. They exhibit several oxidation states.
7. They form alloys with other metals.
8. They form interstitial compounds with elements such as hydrogen, boron, carbon etc.
9. Most of the transition metals such as Mn, Ni, Cr, V, Pt, etc., and their compounds have been used as
good catalyst.
10. There are a total of four series in d-block elements. The first three series contains ten elements in
each one, while the last series is incomplete.
11. First transition series or 3d series corresponding to filling of 3d-subshell with ten elements from
scandium to zinc.
12. Second series or 4d series located in the 5th period contains ten elements from Ytterbium to cadmium.
13. Third series or 5d series located in 6 th period with ten elements from lanthanum to mercury. After
lanthanum (57) there is a gap of 14 elements of lanthanide than next element Hafnium (72) again a
part of d-block element.

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 14. Last series of transition started from actinium (89) after that 14 elements will be part of actinoids than
next element kurchatovium (104) will place in this series. The rest of the elements in this series are
artificial and radioactive in nature.
15. Transition elements contain an incomplete d-subshell, so they show a variable oxidation state. For
example; Osmium (Os) shows a maximum +8 oxidation number and Manganese (Mn) shows +7
oxidation number in potassium per magnate (KMnO4).
16. The atomic radius follows the general trend of the periodic table. When we move in a series from left
to right, the atomic radius first decreases than becomes stable and increases at the end of series. This
trend is due to the screening effect of inner d-electrons.

Electronic configuration
The first row of these is shown in the shortened form of the Periodic Table below.

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The electronic structures of the d block elements shown are:
Sc [Ar] 3d14s2 Fe [Ar] 3d64s2

Ti [Ar] 3d24s2 Co [Ar] 3d74s2

V [Ar] 3d34s2 Ni [Ar] 3d84s2

Cr [Ar] 3d54s1 Cu [Ar] 3d104s1

Mn [Ar] 3d54s2 Zn [Ar] 3d104s2

Transition metal ions

When d-block elements form ions, the 4s electrons are lost first.

To write the electronic structure for Co2+:

Co [Ar] 3d74s2

Co2+ [Ar] 3d7

The 2+ ion is formed by the loss of the two 4s electrons.

To write the electronic structure for V3+:

V [Ar] 3d34s2

V3+ [Ar] 3d2

The 4s electrons are lost first followed by one of the 3d electrons

Oxidation States of Transition Metals

The oxidation state of an element is related to the number of electrons that an atom loses, gains, or appears to
use when joining with another atom in compounds.
It also determines the ability of an atom to oxidize (to lose electrons) or to reduce (to gain electrons) other
atoms or species.
Almost all of the transition metals have multiple potential oxidation states.

Unpaired Electrons of d-orbitals

To fully understand the phenomena of oxidation states of transition metals, we have to understand how the
unpaired d-orbital electrons bond. There are five orbitals in a d subshell manifold. As the number of unpaired
valence electrons increases, the d-orbital increases, the highest oxidation state increases.

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This is because unpaired valence electrons are unstable and eager to bond with other chemical species. This
means that the oxidation states would be the highest in the very middle of the transition metal periods due to
the presence of the highest number of unpaired valence electrons.

To determine the oxidation state, unpaired d-orbital electrons are added to the 2s-orbital electrons since the
3d-orbital is located before the 4s-orbital in the periodic table.

For example:

Scandium has one unpaired electron in the d-orbital.

It is added to the 2 electrons of the s-orbital and therefore the oxidation state is +3.

So that would mathematically look like:

1s electron + 1s electron + 1d electron = 3 total electrons = oxidation state of +3.

The formula for determining oxidation states would be (with the exception of copper and chromium):
Highest Oxidation State for a Transition metal = Number of Unpaired d-electrons + Two s-orbital
electrons
Note: The number of d-electrons range from 1 (in Sc) to 10 (in Cu and Zn).
All transition metals except Sc are capable of bivalency. The 4s electrons are first used and then 3d electrons.

There is a great variety of oxidation states but patterns can be found.

Known oxidation states can be summarized by the table below.

All show oxidation state +2 (except Sc) due to loss of two 4s electrons.
All show +3, but rare in Ni and Cu.
Since, Transition metal ions are small they have a high charge density, therefore, display similar properties to
Aluminium.

Note: Mn can have an oxidation state of +7 due to the hypothetical loss of 7 electrons (4s 2 3d5) - after this
nuclear charge binds electrons more strongly.
Mn has the maximum number of unpaired electrons available for bond formation.
The number of unpaired electron decreases steadily on either side of Mn.

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 Stability of oxidation states

1. Stability of higher oxidation states decreases from left to right. A possible reason is the increase in nuclear
charge.
2. Relative stability of +2 and +3 state

a. The increasing stability of +2 across the period is caused by the greater difficulty of removing
a third electron as nuclear charge increases.
b. Mn2+/Mn3+ and Fe2+/Fe3+ have stabilities that do not fit in this pattern. This can be explained
by the stability of 3d5 found in Fe3+ and Mn2+.

To help remember the stability of higher oxidation states for transition metals it is important to know the
trend:
the stability of the higher oxidation states progressively increases down a group.
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 For example, in group 6, (chromium) Cr is most stable at a +3 oxidation state,
meaning that you will not find many stable forms of Cr in the +4 and +5 oxidation states.
By contrast, there are many stable forms of molybdenum (Mo) and tungsten (W) at +4 and +5 oxidation
states.

Transition metals as catalysts

The ability of transition metals to form more than one stable oxidation state means that they can accept and
lose electrons easily. This enables them to catalyze certain redox reactions. They can be readily oxidized and
reduced again, or reduced and then oxidized again, as a consequence of having a number of different
oxidation states of similar stability. They can behave either as homogeneous catalysts or as heterogeneous
catalysts.

1. How a catalyst works

A catalyst is a substance which alters the rate of a reaction without itself being chemically unchanged at the
end.

A catalyst lowers the activation energy for the reaction by providing an alternative route. An extra step is
introduced.

e
n
uncatalysed reaction
e
(high activatio energy)
r
g reactants
y catalysed reaction
(low activation energy)

products

reaction pathway

Because the activation energy is lower, more particles have enough energy to react when they collide and so
the fraction of successful collisions is higher.

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 2. Homogeneous catalysis

A homogeneous catalyst is a catalyst in the same phase as the reactants.

Homogeneous catalysis involves aqueous transition metal ions catalysing reactions, often between two
anions. The cation reacts with each anion in turn, thus avoiding the need for a direct collision between two
anions (this is difficult since they repel each other).

Example: S2O82-(aq) + 2I-(aq)  2SO42-(aq) + I2(aq)

This can be catalysed by Fe2+ or Fe3+ ions:

With Fe2+: S2O82-(aq) + 2Fe2+(aq)  2SO42-(aq) + 2Fe3+(aq)

2Fe3+(aq) + 2I-(aq)  2Fe2+(aq) + I2(aq)

With Fe3+: 2Fe3+(aq) + 2I-(aq)  2Fe2+(aq) + I2(aq)

2Fe2+(aq) + S2O82-(aq)  2Fe3+(aq) + 2SO42-(aq)

2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq)  2Mn2+(aq) + 10CO2(g) + 8H2O(l)

This is a good example of auto-catalysis.

One of the products in this reaction, Mn 2+(aq), behaves as a catalyst and thus the reaction is slow at first
but is much faster after a little of the products are formed.

3. Heterogeneous catalysis

Heterogeneous catalysts react by allowing the reactant molecules to bond to the surface of the metal, usually
by attracting the surface electrons. The reaction takes place at the surface, and the transition metal regains
electrons as the products leave. The reaction is catalysed because the reactant molecules spend more time in
contact with each other than they would in the absence of a catalyst.

e.g. hydrogenation of ethene

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 H H
H H
C C
H C C
H H
H H H
H H H H H
H
H H C C

Ni Ni Ni

a) Physical adsorption and chemisorption

The molecules usually bond to the surface of the metal using intermolecular forces such as Van der Waal’s
forces. This is known as physical adsorption. Sometimes they actually form a covalent bond with the metal.
This is known as chemisorption.

An ideal heterogeneous catalyst adsorbs fairly strongly but not too strongly. If it adsorbs too weakly (like
silver) the reactant molecules do not spend enough time in contact with each other. If they adsorb too
strongly (like tungsten) the products do not leave the metal surface quickly enough and this slows the
reaction down.

The most useful catalysts are those which adsorb moderately. As the strength of absorption tends to decrease
from left to right along the Periodic Table, the most effective catalysts tend to be the transition metals in the
middle, like V, Fe and Ni.
b) Examples of heterogeneous catalysts
Examples of heterogeneous catalysts are; Fe in the production of ammonia, V 2O5 in the contact process and
Pt or Ni in the hydrogenation of ethene.

i) N2(g) + 3H2(g) == 2NH3(g) Fe catalyst

ii) 2SO2(g) + O2(g) == 2SO3(g) V2O5 catalyst

iii) C2H4(g) + H2(g) == C2H6(g) Pt/Ni catalyst

iv) 2CO(g) + 2NO(g) == N2(g) + 2CO2(g) Rh catalyst

The catalytic converter converts toxic carbon monoxide and nitrogen monoxide to non-toxic carbon
dioxide and nitrogen.

c) Surface area
The catalyst needs to have a large surface area to be effective. This means it needs to be very thinly spread
out, and might need a special support.
Catalytic converters in cars use rhodium (Rh) on a special ceramic support

d) Catalyst poisoning
Heterogeneous catalysts can be poisoned by impurities, which are often present in the raw materials used.
These impurities bond very strongly to the catalyst surface and block it.

The activity of iron in the Haber process is reduced by sulphur, present in iron as an impurity so it is
essential that as much sulphur as possible is removed during the Basic Oxygen Process.
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The efficiency of catalytic converters in cars is reduced by lead, which bonds permanently to the rhodium
surface. This has led to the increased use of unleaded petrol.

More examples
1. Iron in the Haber Process
The Haber Process combines hydrogen and nitrogen to make ammonia using an iron catalyst.



2. Nickel in the hydrogenation of C=C bonds
This reaction is at the heart of the manufacture of margarine from vegetable oils.
However, the simplest example is the reaction between ethene and hydrogen in the presence of a nickel
catalyst.

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 Transition metal compounds as catalysts

3. Vanadium(V) oxide in the Contact Process

At the heart of the Contact Process is a reaction which converts sulphur dioxide into sulphur trioxide.
Sulphur dioxide gas is passed together with air (as a source of oxygen) over a solid vanadium(V) oxide
catalyst.


4. Iron ions in the reaction between persulphate ions and iodide ions
Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful oxidising agents. Iodide ions are very
easily oxidised to iodine. And yet the reaction between them in solution in water is very slow.
The reaction is catalysed by the presence of either iron(II) or iron(III) ions.

Comparison of heterogeneous and homogeneous catalysts

• Usually distinct solid phase • Same phase as reaction medium

• Readily separated • Often difficult to separate
• Readily regenerated and recycled • Expensive/difficult to recycle
• Rates not usually as fast as homogeneous • Often very high rates
• May be difussion limited • Not diffusion controlled
• Quite selective to poisons • Usually robust to poisons
• Lower selectivity • High selectivity
• Long service life • Short service life
• Often high-energy process • Often takes place under mild conditions
• Poor mechanistic understnding • Often mechanism well understood

Difficulties in separation and catalyst regeneration have

prevented a wider use of homogeneous catalysts in industry

Melting and boiling point

Melting and boiling point of these elements are very high (except Zn). These higher values are due to small
atomic radii of transition elements which provides greater inter atomic forces of attraction. They are very
hard.

Conductivity
Transition elements are good conductor of heat and electricity.

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Colour
Except zinc all the transition metals complex ions are coloured due to presence of unpaired electrons.
The colour of ions can be explained on the basis of "Crystal field theory". According to this theory, the
bonding between ligands and a metal ion is electrostatic. The ligands surrounding the metal ion and create an
electrostatic field around its d-orbitals. This field split '5' degenerated d-orbitals in to two sets of different
energies.

(i) A high energy pair (eg) of dx2-dy2 and dz2.

(ii) A low energy trio (t2g) of dxy, dyz, dzx.

In many cases difference of energy between two sets 'eg' and 't2g' is equivalent to a wavelength in the
visible region.
Thus absorbing visible light, an electron may be able to move from lower energy set t2g to higher energy
set eg.

In doing so, some of the component wavelength of white light is removed, so the remaining component
wavelength of light reflected or transmitted shows the colour.

For example: Cu+2 (blue), V+3 (green), Co+2 (pink), Fe+2 (green), Fe+3 (yellow), Ti+3 (purple).

At different oxidation states, same element produce different colours.

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CONCEPTS REVIEW
Periodicity
The recurrence of similar properties of the elements when they are arranged in the
order of increasing atomic number, after certain regular intervals, is called periodicity.

Cause of periodicity of elements

The modern periodic table is based on the electronic configuration of the elements.
The properties of an element are determined largely by the electrons in its outermost
or valence shell. Valence electrons interact with other atoms and take part in all
chemical reactions, while inner shell electrons have little influence on the properties of
elements.
When elements are placed in the order of their increasing atomic number, the
elements having the same number of valence shell electron is repeated in such a way,
so as to fall under the same group. Since, the electronic configuration of the valence
shell electrons is same they show similar properties.

Atomic radii
The size of the atom is significant in governing its property. If the atom is assumed to
be spherical, then the radius of the sphere gives the atomic radius. But it is difficult to
exactly determine the radius of the atom because:
i. The probability of finding the electron is never zero even at large distances from
the nucleus and so the atom does not have a well defined boundary.
ii. It is not possible to isolate an atom and measure its radius.
iii. The size of the atom changes in going from one set of environment to another
and from one bonded state to another.

So, one can arbitrarily define atomic radius as the effective size which is the distance
of closest approach of one atom to another atom in a given bonding situation.
This approximate radius can be determined by measuring the inter-nuclear distance
between the two centres of the neighbouring atoms in a covalent molecule. This is
usually done by diffraction and spectroscopic techniques.

Variation in a period
Atomic radii in general, decrease with increase in atomic number, going from left to
right in a period. This is explained on the basis of increasing nuclear charge along a
period.
The nuclear charge increases progressively by one unit while the corresponding
addition of one electron takes place in the same principal shell. As the electrons in the
same shell do not screen each other from the nucleus, the nuclear charge is not
neutralized by the extra valence electron. Consequently the electrons are pulled closer
to the nucleus by the increased effective nuclear charge resulting in the decrease in
the size of the atom.

Variation in a group
The atomic radii of elements increases from top to bottom in a group because the
nuclear charge increases with increasing atomic number.
Although, there is an increase in the principal quantum number from one atom to
another, the number of electrons in the valence shell remain the same. The effect of

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increase in the size of the electron cloud out weighs the effect of increased nuclear
charge and so the distance of the valence electron from the nucleus increases down
the group. Thus the size of the atom goes on increasing down the group in spite of
increasing nuclear charge.

Ionization Energy
The amount of energy required to remove the most loosely bound electron from an
isolated gaseous atom is called ionization;
The amount of energy required to remove the most loosely bound electron from an
isolated gaseous atom is called ionization energy (IE).
Ionization energy is also called as ionization potential because it is measured as the
minimum potential required to remove the most loosely held. 1 eV per atom = 96.64
kJmol-1 = 23.05 k cal mol-1 .
Thus, the ionization energy gives the ease with which the electron can be removed
from an atom. The smaller the value of the ionization energy, the easier it is to remove
the electron from the atom.

Factors Governing Ionization Energy

i) Size of the atom

As the size of the atom increases the outermost electrons are held less tightly by the
nucleus (attractive force between the electron and the nucleus is inversely
proportional to the distance). As a result it becomes easier to remove the electron and
therefore the ionization energy decreases with the increase in atomic size.

ii) Charge on the nucleus

The attractive force between the nucleus and the electron increases with the increase
in nuclear charge making it more difficult to remove an electron. The ionization energy
thus increases with the increase in the nuclear charge.

iii) Screening effect

In multielectron atoms, the outermost electrons are shielded or screened from the
nucleus by the inner electrons. This is known as shielding or screening effect. The
outer most electrons do not feel the complete charge of the nucleus and the actual
charge felt is called the effective nuclear charge. When the inner electrons are more,
the screening effect will be large, the nuclear attraction will be less. Thus when the
inner electrons increase the ionization energy will decrease.

iv) Penetration effect

The’s’ electrons are more penetrating (maximum probability of finding near the
nucleus) towards the nucleus than the p electrons. The order of penetration power in a
given shell is s > p > d > f.
If the penetration power of the electron is more, it will be closer to the nucleus and will
be held more firmly. Thus ionization energy will increase with the increase in the
penetration power of the electrons. For the same sub shell the ionization energy would
be more to remove an 's' electron than to remove a 'p' electron which in turn will be
more than that for removing a 'd' electron.

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v) Electronic arrangement
Certain electronic configuration like half-filled and completely-filled shells have extra
stability. It is more difficult to remove electron from these stable configuration and the
ionization energy is very high. For example, the noble gases have the most stable
configuration and so have high ionization energy; elements like Be and Mg have
completely filled orbitals while N and P have exactly half-filled sub shells. Thus, their
ionization energies are high. The more stable the electronic configuration, the higher
is the ionization energy.

Successive ionization energies

The energies required to remove subsequent electrons from a gaseous atom is called
as successive ionization energies. They are termed as first, second, third ……
ionization energy depending on the removal of the first, second, third electron
respectively.

The second ionization energies are higher than the first due to the fact that after the
removal of the first electron the atom changes into a monovalent positive ion. In this
ion, the number of electrons decreases but the nuclear charge remains same and so
the remaining electrons are held more tightly by the nucleus and it becomes difficult
to remove the second electron. Hence the value of the second ionization energy (IE 2)
is higher than the first (IE1). In the same way the removal of the second electron will
result in the formation of di-positive ion making the attraction between the nucleus
and the remaining electrons stronger. This results in higher value of third ionization
energy (IE3).

Electron Affinity
Electron affinity is the amount of energy released when an electron is added to an
isolated gaseous atom.
Electron affinity is the ability of an atom to hold an additional electron. If the atom has
more tendency to accept an electron then the energy released will be large and
consequently the electron affinity will be high. Electron affinities can be positive or
negative. It is taken as positive when an electron is added to an atom. It is expressed
as electron volts per atom (eV per atom) or kilo joules per mole.

Factors affecting electron affinity

i) When the nuclear charge is high there is greater attraction for the incoming
electron.
Therefore electron affinity increases as the nuclear charge increases.
ii) With the increase in the size of the atom the electron affinity decreases because the
distance between the nucleus and the incoming electron increases.
iii) Electron affinities are low or almost zero in elements having stable electronic
configurations (half filled and completely filled valence subshells) because of the
small tendency to accept additional electron.

Electronegativity
The relative tendency of an atom in a molecule to attract a shared pair of electrons
towards itself is termed as Electronegativity. The value of electronegativity of an
element describes the ability of its atom to compete for electrons with the other atom

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to which it is bonded. Electronegativity is however not the property of an isolated
atom.
Electronegativity is measured on a number of scale levels, the most commonly used
are of Pauling or Mulliken.
Factors Affecting Electronegativity

i) Atomic size
As the size of the atom decreases it has greater tendency to attract the bonding
electrons towards itself. Therefore smaller atoms have higher electronegativity values
than the larger ones.

ii) Ionisation energy and electron affinity

Higher Ionisation energy and electron affinity lead to higher electronegativity.

iii) Number and nature of atoms

The electronegativity depends on the number and nature of atoms bonded to it.

iv) Type of hybridization

The electronegativity increases with the increase in 's' character in the hybrid orbital.
This is because the 's' orbitals being more near to the nucleus have greater tendency
to attract the shared pair of electron.

v) Charge on the ion

A cation has high electro negativity while an anion has less electro negativity than its
parent atom. A cation with a higher positive charge is more electronegative.

Electropositive or Metallic Character

The tendency of an element to lose electrons and form positive ions (cations) is called
electropositive or metallic character. Elements having low ionization energy are
electropositive. For example alkali metals are the most electropositive elements. The
tendency of an element to lose electrons and form positive ions (cations) is called
electropositive or metallic character. Elements having low ionization energy are
electropositive. For example alkali metals are the most electropositive elements.

Electronegative or Non-metallic Character

The tendency of an element to accept electrons to form an anion is called its non-
metallic or electronegative character. Elements that have high electron affinity (or
high electronegativity) show greater electronegative or non-metallic character. For
example chlorine, oxygen and phosphorous.

Magnetic properties

By the study if electronic configuration of transition metals it is understood that they generally contain one or
more unpaired electrons in the (n-1)d orbital. Due to these unpaired electrons they behave as paramagnetic
substances. These substances are attracted by the magnetic field. The transition elements that contain paired
electrons behave as diamagnetic substances. These substances are repelled by the magnetic field. The
paramagnetic character increases as the number of unpaired electrons increases.

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Formation of colored compounds

Most of the transition elements form colored compounds both in solid state as well as in aqueous solution. It
is already studied that the transition metals have incomplete d-orbital. The electrons are to be promoted from
a lower energy level to a higher energy level. Some amount of energy is required for this process and the
radiations of light are observed in the visible region. The compounds absorb a particular color from the
radiation and the remaining ones are emitted.

For e.g., Cu2+ are bluish green in color due to absorption of red light wavelength.

As Zn has completely filled d-orbitals it cannot absorb radiation and hence Zn2+ salts are white.

Formation of complexes

Transition metals form many complex ions. They are the electrically charged complexes with a metal ion in
the center which is surrounded and linked by a number of neutral molecules or negative ions. These neutral
molecules or negative ions are called as ligands. As the transitions metals are small in size they form large
number of complexes.

Metal are Lewis acids because of their positive charge. When dissolved in water, they react with water to
form hydrated compound such as Na(H2O)6+ and Cu(H2O)62+. These are called metal complexes, or
coordination compounds. These coordination reactions are Lewis acid-base reactions. The Neutral
molecules such as H2O and NH3, and anions such as CN -, CH3COO- are called ligands. The coordination
reaction can be represented by
CuSO4 + 6 H2O = Cu(H2O)62+ + SO42-

Usually, copper sulphate solids are CuSO4*(H2O)5, and its color is light blue. When heated, it loses water of
crystallization, and becomes CuSO4. It is colorless.

Most people know that when ammonia is added to a Cu(H 2O)62+ solution, it turns deep blue. This is due to
the formation of complexes:

Cu(H2O)62+ + 4 NH3 = Cu(H2O)2(NH3)42+ + 4 H2O

Actually, the above reaction takes place in steps. The H 2O molecules are displaced one at a time as the
ammonia concentration, [NH3], increases. As more NH3 is bonded to Cu2+, the blue color deepens.

Ammonia forms complex with many metals. It forms a very strong complex with Ag + such that AgCl solid
will dissolve in ammonia solution.

AgCl (s) + 2 NH3 = Ag(NH3)2+ + 2 Cl-

The silver ammonia complex is colorless, however.

Other commonly encountered ligands are CN-, SCN-, Cl-, ethylene diamine (NH2CH3CH3NH2), and acetate
(CH3COO-). For example,

Fe(H2O)63+ + SCN- = Fe(H2O)5SCN2+ + H2O

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 brown blood red

Electrode potential and low reactivity

The electrode potential is a measure of the total enthalpy change (DHT) when a solid metal, M is brought into
aqueous medium in the form of M+ (aq).

The total enthalpy change depends on sublimation energy, ionization energy and hydration energy of the
metal.

The stability of the oxidation state of metal depends on the electrode potential. When electrode potential is
less the stability is more.

19 | P a g e
F-BLOCK ELEMENTS

F- block elements are also called Inner transition elements. The last electron of these elements enters the 'f'
sub shell. They are mostly radioactive elements. They are present beneath the main periodic table, in the
form of two rows, one row belonging to lanthanides and the other row belonging to actinides.

Lanthanides and Actinides

The first row of the f- block , the 4f series consists of the Lanthanides and the second row, the 5f series are
the Actinides.

Lanthanides Series
Lanthanides or Lanthanones as they are also called, belong to the 4f series, the first series of f- block
elements. In these elements, the differentiating electron enters the 4f- orbitals. This series has
Lanthanum( Z= 57) and the next fourteen elements (Z = 58 to 71). But, La, z = 58 has a completely empty f-
sub -shell. So, the elements from Ce to Lu (58 to 71) usually consists of the lanthanide series.

As the number of electrons in the outermost and the penultimate shell remains the same, the fourteen
elements resemble each other. The lanthanides are also called as rare-earths. The name lanthanides is given
because of the strong resemblance of these elements to lanthanum. The name rare earths was given to these
elements because they were originally extracted from oxides, which were called 'earths' earlier and which
were considered rare.

The 4f electrons of these elements are completely shielded and do not take part in the chemical bonding,
unlike the d- electrons of transition series. These are silvery white metals and are good conductors of heat.
Among all the elements only some elements have a fully filled and half-filled f-orbital. The elements with
these f-orbitals are more stable.

Example : Europium and gadolinium has half-filled f-orbital. Ytterbium and lutetium has fully filled f-
orbital. The list of elements in this series, with atomic number and symbol are

Elements and symbol Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Atomic number 58 59 60 61 62 63 64 65 66 67 68 69 70 71

Groups of lanthanides
Klemm has divided lanthanides into two groups of seven elements each. These are

1. From Cerium Ce(58) to Gadolinium - Gd ( 64)

2. From Terbium (Tb - 65) to Lutetium (Lu - 71)

In the case of the first group, the half filling of 4f orbitals takes place and in the case of second group, the
pairing of electrons in the 'f' sub-shell takes place.

Oxidation States
All the elements of this series exhibit an oxidation state of +3 (Ln 3+ ). Some of these elements also exhibit +2
and +4 states, but these states are not as stable as the +3 state. Only +3 state is exhibited by La, Gd and Lu
20 | P a g e
which is due to extract-ability of empty, completely half filled or completely filled 4f orbitals. Along with
+3, other two oxidation states, +2 and +4 are exhibited by some members of this series.

Example: Eu and Yb can acquire +2 state as it provides them with extra stability.
The Ce4+ ion is stale and it can convert easily to Ce 3+ thereby making the 4+ ion a very strong oxidizing
agent.

Chemical Reactivity
Lanthanides are chemically reactive. They react with carbon, hydrogen, oxygen and sulfur and form
carbides, hydrides, oxides and sulphides respectively. The oxides formed are M 2O3 oxides. They react with
water and form insoluble hydroxides. The oxides and hydroxides react with CO 2and form carbonates,
M2(CO3)3.

Lanthanide Contraction
In moving along the lanthanide series from Ce(58) to Lu (71) a regular decrease in the size of the atom/ion
with increase in atomic number is observed. This decrease in size is called the Lanthanide contraction. In this
series the size of Lanthanum is maximum and that of Lu, lutetium is minimum. The decrease is size, though
continuous, is not regular.

Reason for Lanthanide Contraction

The cause of lanthanide contraction can be traced to the imperfect shielding of one 4f electron by another in
the same sub-shell. On moving along the lanthanide series the number of 4f electrons increases by one unit at
each step and the imperfect shielding increases, causing the contraction in electron cloud of the 4f sub-shell.
Ionic radii changes from 1.06 Α to 0.85A.

Important Consequences
The lanthanide contraction plays a significant role in the chemistry of lanthanides. The important
consequences of it are:

1. There is a steady decrease in ionic size.

2. There is a slight increase in electronegativity of the trivalent ions.
3. The Eo values for M3+ + 3e → M(g) increases regularly from Lanthanum -252V to 2.25 V for
Lutetium.
4. Since there is a very small change in the size of ions in the lanthanide series and there is no change in
the outermost shell, there is a close resemblance in chemical properties.
5. Lanthanide contraction plays a significant role in the chemistry of lanthanides and heavier transition
elements.
6. The atomic radii of 5d transition elements are very close to those of the corresponding 4d transition
elements. Due to this the crystal structure and other properties of lanthanides are very similar.

In these elements the valence electron filled in 4f orbital, hence they are also known as 4f-block elements or first inner
transition element. This series started from Cerium (Ce : Z = 58) ended at lutetium (Lu: Z = 71). Lanthanoides are also known
as "rare earth metals".

21 | P a g e
 Chemical
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Element
Dysp Ytte
Praseo Prom Sam Gado Hol
Lanthanu Ceriu Neo Euro Terb r Erb Thul r Lute
dymiu e a l miu
m m dymium pium ium osiu ium ium biu tium
m thium rium inium m
m m
Atomic
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Number
Melting 135 152 154
920 795 935 1024 1042 1072 826 1312 1407 1461 824 1652
Point(°C) 6 9 5
Atomic
4f75d 4f145d
electron 5d1 4f15d1 4f3 4f4 4f5 4f6 4f7 1 4f9 4f10 4f11 4f12 4f13 4f14 1
config
Ln3+
electron
4f0 4f1 4f2 4f3 4f4 4f5 4f6 4f7 4f8 4f9 4f10 4f11 4f12 4f13 4f14
configuratio
n
Ln3+
radius 103 102 99 98.3 97 95.8 94.7 93.8 92.3 91.2 90.1 89 88 86.8 86.1
(pm)

Applications of Lanthanides

1. Metallurgical applications: Some of the alloys of lanthanide elements find important metallurgical
applications as reducing agents. Example: Misch meals (Ce- 30 to 35%)
2. Ceramic applications: Ce(III) and Ce(IV) oxides find use in glass polishing powders whereas Nd
and Pr oxides are extensively used in coloring glass and in the production of standard light filters.
3. Catalytic applications: Some lanthanide compounds are used as catalysts. Example: Cerium
phosphate is used in petroleum cracking as a catalyst.
4. Electronic applications: The ferromagnetic garnets of 3Ln 2O3.5Fe2O3 type are used in microwave
devices.
5. Nuclear applications: These elements and some of their compounds are used in nuclear control
devices, shielding devices and fluxing devices. Sm - 140, Eu - 153, Gd- 155, Gd- 157 and Dy - 164
are some of the important isotopes used in nuclear technology.

Actinides Elements

The 5f block elements are also called actinoids or actinones. This series includes 15 elements, from
Thorium(Z = 90) to Lawrencium (Z = 103). The name actinides is derived from actinium, the very first
member of the series.

M
Element Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm No Lr
d
Atomic 10 10
89 90 91 92 93 94 95 96 97 98 99 100 103
number 1 2
5f26d17s2 3 1 5f97s2
Electronic 6d1 6d2 5f 6d 5f46d17s2 6 2 7 5f76d1
2 5f10 5f11 5f12 5f13 5f14 5f14
or 5f 7s 5f 7s or
configuration 7s2 7s2 7s2 or 5f57s2 7s 2
7s2 7s2 7s2 7s2 7s2 7s27p1
5f16d27s2 5f86d17s2

22 | P a g e
 Oxidation 3, 4, 5, 3, 4, 5, 6, 3, 4, 5, 6, 2, 3,
3 3, 4 3, 4, 5 3, 4 3, 4 2,3 2,3 2,3 2,3 2,3 3
state 6 7 7 4
Metallic 0.18 0.18
0.203 0.180 0.162 0.153 0.150 0.162 0.173 0.174 0.170
radius,nm 6 6
Temperature
153 83 83
, 1050 1750 1572 1130 640 640 1176 1340 1050 900 860 1630
0 0 0
°C: melting
Density, 13.5
10.07 11.78 15.37 19.06 20.25 19.84 11.7 14.78
g/cm3 1

Some Trends in Properties of the Transition Metals

The electronegativity of the elements increases, and the hydration energies of the metal cations decrease in

magnitude from left to right and from top to bottom of the d block. As a result, the metals in the lower right

corner of the d block are so unreactive that they are often called the “noble metals.”

ORGANOMETALLIC COMPOUNDS

Compounds that contain a metal-carbon bond, R-M, are known as "organometallic" compounds.
Organometallic compounds of Li, Mg (Grignard reagents) are amongst some of the most important organic
reagents. Many other metals have been utilised, for example Na, Cu and Zn.

Organometallic compounds provide a source of nucleophilic carbon atoms which can react with
electrophilic carbon to form a new carbon-carbon bond. This is very important for the synthesis of complex
molecules from simple starting materials.

To rationalize the general reactivity of organometallics it is convenient to view them as ionic, so R-M = R-
M+

The most important reactions is this chapter are the reactions of organolithiums, RLi, and Grignard
reagents, RMgX, with the carbonyl groups in aldehydes, ketones and esters to give alcohols. However, we
will also look at some useful reactions involving Cu, Zn and Hg.

Reactivity:

23 | P a g e
 methyl chloride methyllithium methylmagnesium bromide
CH3Cl CH3Li CH3MgBr
The images show the electrostatic potentials for methyl chloride, methyl lithium and methyl magnesium
bromide.

The more red an area is, the higher the electron density and the more blue an area is, the lower the electron
density.

 In the alkyl halide, the methyl group has lower electron density (blue), and is an electrophile.
 In methyl lithium, the methyl group has higher electron density (red) and is a nucleophile.
 In methyl magnesium bromide, the methyl group is less electron rich that methyl lithium.

Therefore, organometallic compounds react as electron rich or anionic carbon atoms i.e. as carbanions, which
means they will function as either bases or nucleophiles.

It is reasonable to think of these organometallic compounds as R- M+

Basicity:

The following equation represents the loss of

a proton from a generic hydrocarbon forming
a carbanion:

 Organolithium and organomagnesium compounds are strong bases since the negative charge is on
carbon.
 Simple carbanions are strong bases, (see pKa's below) since the C is not very electronegative
(compared to N or O)
 In the presence of weak acids, RLi and RMgX protonate giving the hydrocarbon.

 Implications: RLi or RMgX CANNOT be used in the presence of acidic hydrogens such as -OH, -
NH or -SH units.

Compound Structure pKa The table shows the pKa's of a selection of

2- representative systems. Note that the hydrocarbons
71 are very weak acids, implying that the carbanions
methylpropane
will be strong bases.

24 | P a g e
 ethane 62
methane 60
ethene 45

benzene 43

ammonia 36
ethyne 25
ethanol 16
water 15.7
Preparations of Organometallic Reagents
1. Organolithiums RLi
2. Organomagnesium or Grignards, RMgX
3. Dialkyllithium cuprates, R2CuLi
4. Organozinc reagents, RZnX
5. Acetylides, RC≡CM

1. Synthesis of Organolithiums RLi

In general, this is a redox reaction in the form of;

Organolithiums are formed by the reaction of alkyl halides with lithium metal.
e.g.
Cl Li
+ 2Li
+ LiCl

Typical solvents are normally anhydrous diethyl ether but pentane or hexane can also be used.
The alkyl group can be primary, secondary or tertiary.
Halide reactivity: I > Br > Cl
R can be alkyl, vinyl or aryl
Other Group I metals (Na, K) can be used instead of Li.

2. Synthesis of Organomagnesium Reagents

This is a redox reaction in the form of;

Organomagesiums are formed by the reaction of alkyl halides with magnesium metal.
Typical solvents are normally anhydrous diethyl ether or tetrahydrofuran.
The alkyl group can be primary, secondary or tertiary.
Halide reactivity : I > Br > Cl
R can be alkyl, vinyl or aryl.

25 | P a g e
The Grignard reaction is one of the characteristic reactions of carbonyl compounds. It is especially useful as
a means of forming new carbon-carbon bonds, something that we haven't seen much of until now. In this
type of reaction a C-M bond is present (C=carbon and M=metal) which is covalent in nature. The metal is
usually magnesium but lithiummore reactive and is also used. The more polar the C-M bond is, the more will
be its reactivity. The reactivity order is known from electrochemical series:
M= Li> K> Ca> Na> Mg> Al> Zn> Fe> Sn etc
Traditionally alkyl magnesium halides are known as Grignard reagent (R-Mg-X).

Mechanism of Grignard reagent:

The mechanism of Grignard reagent (GR) is not clear till today, but it is believed that the reaction is taking
place on the metal surface. Since GR does not react with aprotic solvents (e.g. ether, THF etc), these solvents
are widely used. The mechanism of formation of GR as follows: it goes via one electron transfer, followed
by rapid combination of organic group with the metal center. From the mechanistic point of view, carbon-
bromine bond should be broken prior to the reaction with magnesium.

Solutions of some Grignard reagents such as methylmagnesium bromide, ethylmagnesium bromide, and
phenylmagnesiumbromides are commercially available. Here is an example of Grignard reaction which
explains the effect of solvent.

26 | P a g e
The Grignard reagent is made from the direct reaction of magnesium with an alkyl halide.

The key to the function of the Grignard reagent is the reversal of the normal polarity of bonds to carbon
(This type of reversal of polarity in carbon center is known as Umpolung). Because magnesium is more
electropositive than carbon the carbon acquires aδ− charge whereas carbon, when it has a charge at all,
usually has δ+ charge from bonding to halogens, oxygen, and nitrogen.

This δ−carbon consequently has significant nucleophilic character. The Grignard reagent reacts well as a
nucleophile with the δ+-carbon of the carbonyl group as a target. The C=O π-bond is broken and the
carbonyl becomes an alcohol. In the process, a new carbon-carbon bond is formed between the Grignard
reagent and the carbonyl carbon - now the alcohol carbon.

The intermediate alkoxymagnesium salt is neutralized by acid in the work-up to produce the alcohol product.
Before we go on to look at more Grignard reactions with carbonyl groups, here is a problem for you to try.

1. Identify the product (A-E) (5 points)

Answer:
27 | P a g e
28 | P a g e
3. Synthesis of Organocopper Reagents

Summary

1. The most useful organocopper reagents are lithium dialkylcuprates, R2CuLi.

2. Lithium dialkylcuprates are formed by the reaction of 2 equivalents of an organolithium with a
copper (I) halide.
3. Typical solvents are normally anhydrous diethyl ether or tetrahydrofuran.
4. The alkyl group is usually primary. Secondary and tertiary are prone to decomposition.
5. Halide reactivity : I > Br > Cl
6. R can be alkyl, vinyl or aryl.

4. Preparation of Organozinc Reagents

Summary
Organozinc reagents, RZnX, are prepared in a fashion analogous to that of organomagnesium
reagents RMgX.
They are much less reactive than either RLi or RMgX to aldehydes and ketones.
The most common application of organozinc reagents is in the Simmons-Smith reaction

5. Preparation of Acetylenic Reagents

Summary
A terminal acetylenes can be deprotonated using sodium amide, NaNH2

Acetylenic Grignard reagents, RC≡CMgX, can also be prepared.

Rather than starting from the acetylenic halides, they are prepared by an acid-base reaction of the
terminal acetylene with a second Grignard reagent.
Acetylenic Grignards react in a similar fashion to other Grignard reagents.

29 | P a g e
Using acetylene to build alkynes
Acetylene is the ultimate carbon building block. It bears two relatively acidic C-H bonds (pKa 25) and can
therefore be “alkylated” (i.e. deprotonated to give its conjugate base, then treated with an alkyl halide) on
either end giving either a mono-substituted (also known as a “terminal” alkyne) or di-substituted (“internal”)
alkyne as desired.

RETROSYNTHESIS: How to Plan a Synthesis

"Retrosynthesis" means planning a synthesis backwards, by starting

at the product, the "target" and taking it back a step at a time to
simple, available starting materials or precursors.

In general the process requires "thinking backwards", good problem

solving skills, and a good knowledge of their organic reactions.

In order to "plan" a synthesis, we can break the target down by

making a series of "disconnections" - these steps are the reverse of
synthetic steps or reactions.

30 | P a g e
METAL CARBONYLS

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal
carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis

In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometalic
complexes.
Metal carbonyls are toxic by skin contact, inhalation or ingestion, in part because of their ability to
carbonylate hemoglobin to givecarboxyhemoglobin, which prevents the binding of O2

Carbonyl compounds may be polynuclear or mononuclear

Nomenclat
ure
The nomenclature of the metal carbonyls depends on;
i. the charge of the complex,
ii. the number and type of central atoms,
iii. the number and type of ligands and their binding modes.

31 | P a g e
They occur as
i. neutral complexes,
ii. positively charged metal carbonyl cations
iii. negatively charged metal carbonylates.

The carbon monoxide ligand may be bound

i. terminally to a single metal atom or
ii. bridging to two or more metal atoms.

These complexes may be homoleptic, that is containing only CO ligands, such as nickel carbonyl(Ni(CO)4),
but more commonly metal carbonyls are heteroleptic and contain a mixture of ligands.

The number of carbon monoxide ligands in a metal carbonyl complex is described by a Greek numeral,
followed by the word carbonyl.
Carbon monoxide has different binding modes in metal carbonyls. They differ in the hapticity and the
bridging mode.
The hapticity describes the number of carbon monoxide atoms, which are directly bonded to the central
atom. The denomination shall be made by the letter η n, which is prefixed to the name of the complex. The
superscript n indicates the number of bounded atoms.
In monohapto coordination, such as in terminally bonded carbon monoxide, the hapticity is 1 and it is usually
not separately designated.
If carbon monoxide is bound via the carbon atom and via the oxygen to the metal, it will be referred to as
dihapto coordinated η2.
The carbonyl ligand engages in a range of bonding modes in metal carbonyl dimers and clusters. In the most
common bridging mode, the CO ligand bridges a pair of metals. This bonding mode is observed in the
commonly available metal carbonyls: Co2(CO)8, Fe2(CO)9, Fe3(CO)12, and Co4(CO)12.
In certain higher nuclearity clusters, CO bridges between three or even four metals. These ligands are
denoted μ3-CO and μ4-CO. Less common are bonding modes in which both C and O bond to the metal, e.g.
μ3-η2.

Examples

32 | P a g e
33 | P a g e
Structure and bonding
The HOMO of CO is a σ MO

O
CO atomic
molecular orbitals
orbitals

The LUMO of CO is a π* antibonding MO

Carbon monoxide bonds to transition metals using "synergistic π* back-bonding."

The bonding has three components, giving rise to a partial triple bond.
i. A sigma bond arises from overlap of nonbonding sp-hybridized electron pair on carbon with a
blend of d-, s-, and p-orbitals on the metal.
ii. A pair of π bonds arises from overlap of filled d-orbitals on the metal with a pair of π-antibonding
orbitals projecting from the carbon of the CO.
The latter kind of binding requires that the metal have d-electrons, and that the metal is in a relatively low
oxidation state (<+2) which makes the back donation process favorable. As electrons from the metal fill the
π-antibonding orbital of CO, they weaken the carbon-oxygen bond compared with free carbon monoxide,
34 | P a g e
while the metal-carbon bond is strengthened. Because of the multiple bond character of the M-CO linkage,
the distance between the metal and carbon is relatively short, often < 1.8 Â, about 0.2 Â shorter than a metal-
alkyl bond.
Several canonical forms can be drawn to describe the approximate metal carbonyl bonding modes.

Resonance structures of a metal carbonyl, from left to right the contributions of the right-hand-side canonical
forms increase as the back bonding power of M to CO increases.

Synthesis
Direct reaction of metal with carbon monoxide
Nickel tetracarbonyl and iron pentacarbonyl can be prepared according to the following equations by
reaction of finely divided metal with carbon monoxide:
Ni + 4 CO → Ni(CO)4 (1 bar, 55 °C)
Fe + 5 CO → Fe(CO)5 (100 bar, 175 °C)

Reduction of metal salts and oxides

Some metal carbonyls are prepared by the reduction of metal halides in the presence of high pressures of
carbon monoxide under pressure. A variety of reducing agents are employed,
including copper, aluminum, hydrogen, as well as metal alkyls such as triethylaluminum. Illustrative is the
formation of chromium hexacarbonyl from anhydrouschromium(III) chloride in benzene with aluminum as a
reducing agent, and aluminum chloride as the catalyst:
CrCl3 + Al + 6 CO → Cr(CO)6 + AlCl3
The use of metal alkyls, e.g. triethylaluminium and diethylzinc as the reducing agent leads to the oxidative
coupling of the alkyl radical to the dimer:
WCl6 + 6 CO + 2 Al(C2H5)3 → W(CO)6 + 2 AlCl3 + 3 C4H10
Tungsten, molybdenum, manganese, and rhodium salts may be reduced with lithium aluminum
hydride. Vanadium hexacarbonyl is prepared with sodium as a reducing agent inchelating solvents such
as diglyme.
VCl3 + 4 Na + 6 CO 2 diglyme → Na(diglyme)2[V(CO)6] + 3 NaCl
[V(CO)6]− + H+ → H[V(CO)6] → 1/2 H2 + V(CO)6
In aqueous phase nickel or cobalt salts can be reduced, for example, by sodium dithionite. In the presence of
carbon monoxide, cobalt salts are quantitatively converted to the tetracarbonylcobalt(-1) anion:
Co2+ + 1.5 S2O42− + 6 OH− + 4 CO → Co(CO)4− + 3 SO32− + 3 H2O
Some metal carbonyls are prepared using CO as the reducing agent. In this way, Hieber and Fuchs first
prepared dirhenium decacarbonyl from the oxide:
Re2O7 + 17 CO → Re2(CO)10 + 7 CO2

35 | P a g e
If metal oxides are used carbon dioxide is formed as a reaction product. In the reduction of metal chlorides
with carbon monoxide phosgene is formed, as in the preparation of osmium carbonyl chloride from the
chloride salts.
Carbon monoxide is also suitable for the reduction of sulfides, where carbonyl sulfide is the byproduct.

Photolysis and thermolysis

Photolysis or thermolysis of mononuclear carbonyls generates bi- and multimetallic carbonyls such as diiron
nonacarbonyl (Fe2(CO)9). On further heating, the products decompose eventually into the metal and carbon
monoxide.
2 Fe(CO)5 → Fe2(CO)9 + CO
The thermal decomposition of triosmium dodecacarbonyl (Os 3(CO)12) provides higher-nuclear osmium
carbonyl clusters such as Os4(CO)13, Os6(CO)18 up to Os8(CO)23.
Mixed ligand carbonyls of ruthenium, osmium, rhodium, and iridium are often generated by abstraction of
CO from solvents such as dimethylformamide (DMF) and 2-methoxyethanol. Typical is the synthesis
of IrCl(CO)(PPh3)2 from the reaction of iridium(III) chloride and triphenylphosphine in boiling DMF
solution.

Salt metathesis
Salt metathesis reaction of for example KCo(CO)4 with [Ru(CO)3Cl2]2 leads selectively to mixed-metal
carbonyls such as RuCo2(CO)11.
KCo(CO)4 + [Ru(CO)3Cl2]2 → 2 RuCo2(CO)11 + 4 KCl

Metal carbonyl cations and carbonylates

The synthesis of ionic carbonyl complexes is possible by oxidation or reduction of the neutral complexes.
Anionic metal carbonylates can be obtained for example by reduction of dinuclear complexes with sodium.
A familiar example is the sodium salt of iron tetracarbonylate (Na 2Fe(CO)4,Collman's reagent), which is
used in organic synthesis.
The cationic hexacarbonyl salts of manganese, technetium and rhenium can be prepared from the carbonyl
halides under carbon monoxide pressure by reaction with a Lewis acid.
Mn(CO)5Cl + AlCl3 + CO → Mn(CO)6+AlCl4−
The use of strong acids succeeded in preparing gold carbonyl cations such as [Au(CO) 2]+, which is used as a
catalyst for the carbonylation of olefins. The cationic platinum carbonyl complex [Pt(CO) 4]+ can be prepared
by working in so-called super acids such as antimony pentafluoride

Carbonyl Related compounds

Many analogues of CO ligands are known to form homoleptic and mixed ligand complexes.

36 | P a g e
Complexes of nitrosyls
Metal nitrosyls, featuring NO as a ligand are numerous, although homoleptic derivatives are not. Relative to
CO, NO is a stronger acceptor and isocyanides are better donors. Well known nitrosyl carbonyls include
CoNO(CO)3 and Fe(NO)2(CO)2.

Complexes of thiocarbonyls
Complexes containing CS are known but are uncommon. The rarity of such complexes is attributable in part
to the fact that the obvious source material, carbon monosulfide, is unstable. Thus, the synthesis of
thiocarbonyl complexes requires more elaborate routes, such as the reaction of disodium tetracarbonylferrate
with thiophosgene

Na2Fe(CO)4 + CSCl2 → Fe(CO)4CS + 2 NaCl

Complexes of CSe and CTe are very rare.

Complexes of PF3
Complexes of PF3 often parallel those of the metal carbonyls. In contrast to PF 3, alkyl- and arylphosphines
can be substituted for CO in metal carbonyls, but rarely give homoleptic complexes analogous to the
carbonyls.

Complexes of isocyanides
Isocyanides also form extensive families of complexes that are related to the metal carbonyls. Typical
isocyanide ligands are MeNC and t-butylisocyanide ((Me3CNC). A special case is CF3NC, an unstable
molecule that forms stable complexes whose behavior closely parallels that of the metal carbonyls.

37 | P a g e
ELECTRON RULE

The 18-Electron Rule (also the EAN rule, or Effective Atomic Number)

Stable organometallic compounds of the transition elements will have a total of 18 valence electrons.
Molecules with 16 electrons are sometimes stable (especially in square-planar complexes) and are often
intermediates in organometallic reactions.

There are two formalisms for counting valence electrons in an organometallic complex. One is the neutral
ligand, and the other is the charged ligand, formalism. We will cover only the neutral ligand formalism, in
order to avoid mixups. [Text describes both, this one is "method B."]

To count valence electrons in a metal complex:

1. count the valence electrons of the neutral metal

2. count the electrons contributed from each ligand to bonding
3. count the overall charge on the compound
4. add them all up.

Common ligand types and the number of electrons they contribute are shown in handout.

Examples:

Ni(CO)4:
Ni 10 e—
4 CO's 8 e—
18 e—

CH3Mn(CO)5:
Mn 7 e—
5 CO-s 10e—
CH3 1 e—
18 e—

Stable complexes with fewer than 18 electrons are called electronically unsaturated, and if they have fewer
than 6 ligands they are sometimes called coordinatively unsaturated. This tends to mean that they would
also be happy with more electrons, and/or more ligands, respectively.

III. Metal Carbonyl Complexes

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal
carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis,
such as hydroformylation and Reppe chemistry. In the Mond process, nickel carbonyl is used to produce
pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other
organometalic complexes.
Metal carbonyls are toxic by skin contact, inhalation or ingestion, in part because of their ability to
carbonylate hemoglobin to givecarboxyhemoglobin, which prevents the binding of O2.
38 | P a g e
Nomenclature
The nomenclature of the metal carbonyls depends on the charge of the complex, the number and type of
central atoms, and the number and type of ligands and their binding modes. They occur as neutral
complexes, as positively charged metal carbonyl cations or as negatively charged metal carbonylates. The
carbon monoxide ligand may be bound terminally to a single metal atom or bridging to two or more metal
atoms. These complexes may be homoleptic, that is containing only CO ligands, such as nickel
carbonyl(Ni(CO)4), but more commonly metal carbonyls are heteroleptic and contain a mixture of ligands.
Mononuclear metal carbonyls contain only one metal atom as the central atom. Except Vanadium
hexacarbonyl only metals with even order number such as chromium, iron, nickel and their homologs build
neutral mononuclear complexes. Polynuclear metal carbonyls are formed from metals with odd order
numbers and contain a metal-metal bond. Complexes with different metals, but only one type of ligand will
be referred to as isoleptic.
The number of carbon monoxide ligands in a metal carbonyl complex is described by a Greek numeral,
followed by the word carbonyl. Carbon monoxide has different binding modes in metal carbonyls. They
differ in the hapticity and the bridging mode. The hapticity describes the number of carbon monoxide atoms,
which are directly bonded to the central atom. The denomination shall be made by the letter η n, which is
prefixed to the name of the complex. The superscript n indicates the number of bounded atoms. In
monohapto coordination, such as in terminally bonded carbon monoxide, the hapticity is 1 and it is usually
not separately designated. If carbon monoxide is bound via the carbon atom and via the oxygen to the metal,
it will be referred to as dihapto coordinated η2.
The carbonyl ligand engages in a range of bonding modes in metal carbonyl dimers and clusters. In the
most common bridging mode, the CO ligand bridges a pair of metals. This bonding mode is observed in the
commonly available metal carbonyls: Co2(CO)8, Fe2(CO)9, Fe3(CO)12, and Co4(CO)12. In certain higher
nuclearity clusters, CO bridges between three or even four metals. These ligands are denoted μ 3-CO and μ4-
CO. Less common are bonding modes in which both C and O bond to the metal, e.g. μ3-η2.

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Structure and Bonding:

The HOMO of CO is a σ MO

Energy level scheme of the σ and π orbitals of carbon monoxide

The LUMO of CO is a π* antibonding MO

Carbon monoxide bonds to transition metals using "synergistic π* back-bonding." The bonding has three
components, giving rise to a partial triple bond. A sigma bond arises from overlap of nonbonding sp-
hybridized electron pair on carbon with a blend of d-, s-, and p-orbitals on the metal. A pair of π bonds
arises from overlap of filled d-orbitals on the metal with a pair of π-antibonding orbitals projecting from
the carbon of the CO.

The latter kind of binding requires that the metal have d-electrons, and that the metal is in a relatively
low oxidation state (<+2) which makes the back donation process favorable. As electrons from the metal
fill the π-antibonding orbital of CO, they weaken the carbon-oxygen bond compared with free carbon
monoxide, while the metal-carbon bond is strengthened.

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 Because of the multiple bond character of the M-CO linkage, the distance between the metal and carbon
is relatively short, often < 1.8 Â, about 0.2 Â shorter than a metal-alkyl bond. Several canonical
forms can be drawn to describe the approximate metal carbonyl bonding modes.

Resonance structures of a metal carbonyl, from left to right the contributions of the right-hand-side
canonical forms increase as the back bonding power of M to CO increases.

Stabilized by M —> L backbonding (d —> p*). Remember the HOMO and LUMO of CO;
there is a combination of L—>M sigma bonding and M—>L pi back-bonding. For the M—>L pi back-
bonding you need an electron-rich metal (low oxidation state).
This effect is mirrored in the trends of CO stretching frequencies--high back-bonding causes more electron
density in CO p* orbital, weakening C—O bond, lowering stretching frequency. e.g.
Ni(CO)4 2046 cm-1
Co(CO)4— 1883 cm-1
2—
Fe(CO)4 1788 cm-1

With increasing charge on the metal, greater pi donation, lowering CO bond order.

Polynuclear metal carbonyls are common and may contain metal-metal bonds as in Mn 2(CO)10, and/or
bridging CO groups as in

Fe2(CO)9.

 Bridging CO's have lower C—O stretching frequencies (v ~ 1800 cm -1) than terminal CO's (v ~ 2000
cm-1). Note, however, that the electron count alone does not predict presence of bridging CO's since
an M2(CO)2 unit has the same number of electrons either way.
 Number of carbonyl bands in IR is diagnostic "fingerprint" of CO substitution (see table 13-7, p505).

IV. Synthesis of Metal Carbonyls

Direct Synthesis:

Ni(s) + CO (g) —> Ni(CO)4 clear liquid, bp 43 C, mp -25 C

Co(s) + CO(g) —> Co2(CO)8 orange solid, mp 51 C, 98%

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(requires harsh conditions: 150 C, 200 atm pressure)

Reductive Carbonylation:

CrCl3 + Al(s) + CO + AlCl3 —> Cr(CO)6 + AlCl3 white solid, 88%, mp 154 C
Mn(OAc)2 + (iBu)3Al + CO —> Mn2(CO)10 48%, yellow solid, mp 152 C
(requires 140 C, 20 hours)

Cluster Formation:

Cr(CO)6 + PPh3 --> Cr(CO)5(PPh3) + CO (thermal or photochemical)

IV. Common Reactions of Metal Carbonyls

Substitution:

Ni(CO)4 + PF3 —> Ni(CO)3PF3 + CO (dissociative mech)

Cr(CO)6 + C6H6 —> (h6-C6H6)Cr(CO)3 + 3 CO

In this context, steric/electronic effects can be important; "cone angles"--degree of substitution is often
determined by size of L. Rate of CO substitution decreases as more strongly basic ligands replace CO
(strengthen M-C bond by p-backbonding, which stabilizes starting material compared to transition state).

Reduction:

Fe(CO)5 + Na/thf —> Na2[Fe(CO)4] + CO

(mononuclear; loss of CO)
(CO)5Mn—Mn(CO)5 + Na —> Na2[Mn(CO)5]
(polynuclear organometallics; M-M bond cleavage)
(metal oxidation state changes from zero to -2)
Such anions are easily protonated to form metal hydrides: Bronsted acidity decreases on descending a group.

Oxidation:

(CO)5Mn—Mn(CO)5 + Br2 —> 2 Mn(CO)5Br

(note metal ox. state changes here from 0 to +1)
(CO stretching frequency is higher for Mn(CO)5Br)

Reactions at Coordinated CO:

Most common; formation of metal carbenes:

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V. Other Pi-Acceptor Ligands

isoelectronic series (order is increasing p-donation):

CN— < NºN < CºN-R < CºS < NºO+

How is this determined? Use trans effect to CO: CO frequency is lower if trans ligand is a less
effective p acceptor.

PY3: can "tune" donor/acceptor ability based on nature of Y, e.g.

if Y = F, as in PF3, good pi acceptor (like CO)
if Y = C2H5, as in PEt3, good s donor
You can use a range of substituents, such as halide, alkoxy, amide, alkyl, aryl...

VI. Hydrocarbon Ligands

Hydride:

The hydride ligand, —H, is not a carbon so a metal hydride MH n is not strictly organometallic; but it is often
considered organometallic anyway. The ligand —H is sometimes treated as the simplest possible alkyl
ligand (C0) (also a one-electron donor).

Whether the hydrogen is acidic or not, it is called a "hydride" and treated as H – (when determining the metal
oxidation state). In fact you can make metal hydrides sometimes by reacting a metal complex with an acid,
such as

Cp2Fe + HBF4 —> [Cp2Fe—H+][BF4—]

Metal hydrides can also be made via oxidative addition of HX. As with most ligands in transition metal
chemistry, hydrides can be terminal or bridging.

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Alkyl:

Alkyl ligands have M—C single bonds, and are treated as one electron donors, h1 coordination, R— in
determining oxidation state. Metal-alkyl complexes were difficult to make for the first time b/c they will
readily undergo β-hydrogen elimination:

LnM—CH2CH3 —> LnM—H + CH2=CH2

CpFe(CO)(PPh3)(CH2CH3) + D —> CpFe(CO)(PPh3)(H) + C2H4

One way to get around this is to use alkyl ligands that don't have any b-hydrogens available, for example.
For example, methyl, perfluoroalkyl, tert-butyl, etc. The reverse reaction is called olefin insertion, and that
also occurs in some complexes.

The presence of an agostic interaction (an attractive non-bonding interaction) between the metal and the beta
hydrogen favors b-elimination.

VI. Hydrogen Ligands

Again, although not a carbon-containing ligand, this can be viewed as the "simplest model" for unsaturated
hydrocarbons. The sigma bonding MO of H2 can act as a s donor, while the antibonding H2 MO acts as
a p acceptor (note that the H2 is side-bound to the metal.) In the case where there is significant backbonding
into the H2 antibonding orbital, the H-H bond will lengthen, up to the point where the bond can break
entirely and you would now have two hydride ligands.

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 Metal-Metal Bonding

There are three general classes of M-M bonding:

Covalent: Electron precise bonds. M-M bond counts as one e- from each metal center. Most common
type of M-M bonding.

Dative: Where one metal uses a filled d orbital “lone pair” to coordinate to an empty orbital on a
second, more unsaturated metal. Most dative bonding situations can also be electron-counted
as covalent bonds.

Symmetry: Weak metal-metal interactions caused by molecular orbital symmetry interactions of filled &
empty M-M bonding and/or antibonding orbitals.

Typically seen for d8 metals. Not at all common.

Overlap of d orbitals to make different types of covalent M-M bonding interactions (strongest to weakest):

dz 2 

dyz


dxz

dxy 
the dx2- y2 orbitals (not shown) are used for M-L bonding

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A qualitative MO diagram for the interaction of two square planar metal centers showing the M-M bond
forming interactions:

L M
L
L 
L
L
L
M
L
L  M-M antibonding
orbitals


dz2 dyz dxy dxy dyz dz2
dxz  dxz

the d x2-y2, s and px,y

 M-M bonding
orbitals are not shown orbitals
since they are used
for M-ligand bonding

As one fills the lower energy M-M bonding orbitals, one makes one M-M bond for each pair of electrons
added (one per metal). But once you add more than 8 e- the antibonding orbitals begin to fill and this
starts canceling out M-M bonds.

Electron Count Resulting M-M Bond

d1 - d1 Single bond

d2 - d2 Double bond

d3 - d3 Triple bond

d4 - d4 Quadruple bond optimum

d5 - d5 Triple bond

d6 - d6 Double bond (M-L bonding usually dominates)

d7 - d7 Single bond

d8 - d8 No bond (symmetry interaction)

Note that the table on the previous page specifically refers to two square-planar metals interacting as
shown in the MO diagram. Metal centers with other geometries can often adopt M-M bond orders
different from that shown in the table. Electron-counting can often provide some guidance on this.
Although, if you don’t have any d electrons, you generally can’t have any M-M bonding. Nor can you

46 | P a g e
have a higher M-M bond order than the # of d electrons being shared between the metal centers. For
2
example, two d metals could only form a maximum of a M=M double bond.

Some Covalent Multiple Bonded Examples:

Double Bonds
R
t-Bu t-Bu
O O R
Cl Cl
Cl Cl O O
Ta Ta Cl Os Os Cl
O O
O Cl Cl O
R O O

R
Ta=T a = 2.68 Å Os=Os = 2.30 Å

Triple Bonds
d 5-d 5 Tr iple Bond
Chisholm d 3-d 3 Tr iple Bonds
O
PhH2C OC C
CH2Ph
PhH2 C
Mo Mo Cr Cr
CH2 Ph
PhH2C C C
CH2Ph O O

Mo-Mo = 2.17 Å Cr-Cr = 2.27 Å

Quadruple Bonds (Cotton)

4 4
d -d electronic configurations often lead to the formation of quadruple M-M bonds.

H3C CH3 2-
H3C Re CH3

H3C CH3
Me Me Re
O O
4 H3C CH3
Cr Cr

Cr-Cr = 1.85 Å Re-Re = 2.18 Å

2
This is clearly illustrated above for the non-bridged [Re 2(CH3)8] complex. There is clear steric
repulsion between the methyl groups that could be relieved by rotation to a staggered geometry. But the

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∂-bond component of the quadruple bond favors an eclipsed orientation and imposes a rotational barrier
for rotations about the quadruple bond.

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Dative M-M Bonds (unsymmetrical M-M bonded complexes)
When a metal center with at least two d electrons and a moderately high electron count (16 or 18e-) is
adjacent to a metal that is unsaturated and electron-deficient, the more electron-rich metal center can
donate a lone pair of d electrons to the unsaturated metal to form what is called a dative M-M bond. This
is usually indicated by using an arrow ( ) instead of a line for a covalent bond.

Consider the following bimetallic nickel complex:

t-Bu t-Bu
Ni-P = 2.16 Å Ni-P = 2.24 Å
P
planar coordination CO tetrahedral coordination
like Ni(+2) OC Ni Ni like Ni(0)
CO
P
Ni-CO = 1.70 Å Ni-CO = 1.78 Å
t-Bu
t-Bu

Ni-Ni = 2.41 Å

There are two ways of viewing this electronically (see table below) symmetrically dividing the +2 charge
9
on the nickels needed to balance the two anionic phosphide ligands giving you two d Ni(+1) oxidation
state metals, a covalent Ni-Ni bond, and 16 and 18e- metal centers.

Covalent M-M Bonding Dative

Left Ni Right Ni Left Ni Right Ni

Ni(+1) d9 Ni(+1) d9 Ni(+2) d8 Ni(0) d10

[-PR2] 2e- [-PR2] 2e- 2[-PR2] 4e- 2-PR2 4e-

-PR2 2e- -PR2 2e- CO 2e- 2CO 4e-

CO 2e- 2CO 4e- Ni←Ni(0) 2e-

M-M 1e- M-M 1e-
Total 16e- Total 18e- Total 16e- Total 18e-

10
The other method is to note that the one nickel has tetrahedral coordination geometry, just like a d
8
Ni(0) center, while the other nickel has a planar geometry similar to a d Ni(+2) center. One can “assign”
the two negatively charged phosphide ligands with the Ni(+2) center and have them acting as “neutral”
2e- donors to the Ni(0) center. This then gives one an 18e- Ni(0) center and a three-coordinate 14e-
10
Ni(+2) center. Let the electron-rich, 18e- d Ni(0) center donate one of its’ lone pairs to the unsaturated
8 8
14e- d Ni(+2) bringing it up to 16e-, which is a normal electron-count for a square-planar d Ni(+2)
atom.

49 | P a g e
Note that we get the same electron count and some sort of Ni-Ni bond via either method. So you
generally don’t have to worry about which method you use. Obviously, the covalent method is simpler.

The reason that many consider the dative M-M bond method to be more “accurate” is that if both nickel
atoms are classified as Ni(+1), why don’t both have the same geometry? One could explain the
differences in geometry & structural features simply because one Ni has an extra CO coordinated and we
will have an electronically unsymmetrical complex regardless of the oxidation state assignments.

Problem: Electron-count the following complex using both the covalent and dative M-M bonding
methods:

R2
Me3P
P CO CO
Me3P
W Re
CO
Me3P
CO OC CO

Weak M-M Interactions by Symmetry

8 8
Based on the MO diagram at the beginning of this section, d -d systems shouldn’t have any M-M
bonding due to the filling of all the M-M antibonding orbitals, which cancels out the M-M bonding
orbitals.

8
More than a few bi- or polymetallic d complexes do show the presence of weak M-M bonding
interactions, both in solution and the solid-state.

+
For example, the Rh and Ir tetrakis(isocyanide) complexes, [M(CNR) 4] , form oligomeric M-M bonded
stacks in solution and in the solid-state, in spite of the fact that there should be no covalent M-M bonds.

weak M-M interactions were caused by a molecular orbital symmetry interaction between the filled -M-
M bonding and *-anti-bonding orbitals with the empty p z  and * orbitals. The empty orbitals are

50 | P a g e
pushed up in energy and the filled orbitals down in energy by this symmetry interaction. This generates a
weak M-M bond – strong enough, however, to allow these complexes to form M-M bonds even in
solution. This orbital effect is shown in the MO diagram to the right.

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 METAL CLUSTERS

A compound in which two or more metal atoms are bonded to one another. Metal cluster
compounds bridge the gap between the solid-state chemistry of the metals—or their lower-valent
oxides, chalcogenides, and related salts—and the complexes of the metals in which each metal
ion is completely surrounded by and bonded to a set of ligands or ions. The latter group
comprises the classical coordination chemistry of metal ions.

The main cluster types are "naked" clusters (without stabilizing ligands) and those with ligands.
Typical ligands that stabilize clusters include carbon monoxide, halides, isocyanides, alkenes,
and hydrides.

Metal cluster compounds contain metal-metal bonds. The focus here is on compounds having
three or more metals in a closed array. Carbon monoxide is the most common ligand in
organometallic cluster compounds, but many other organometallic ligands are bound to clusters,
and the presence of several metals leads to bonding arrangements for the ligand that are not
possible for monometallic.

A variety of metal arrays are seen in cluster compounds. Triangular, tetrahedral, and octahedral
clusters are common, and much larger metal arrays are known. The structures of many clusters,
which can be precisely determined by single-crystal X-ray diffraction, provide some clues to the
way in which ligands are bound to the surfaces of bulk metal particles. The latter are more
difficult to structurally characterize than are molecular clusters.

For many d-block clusters there is a strong correlation between their structure and the number of
valence electrons (from the metal atoms and the ligands). This set of correlations for clusters is
52 | P a g e
similar to the 18-electron rule for mononuclear organometallics, and these guidelines are often
called Wade’s rules after the British chemist Kenneth Wade, who first recognized that a
triangular cluster such as Ru3(CO)12 usually has 48 valence electrons, a tetrahedron such as
Co4(CO)12 has 60 electrons, and an octahedron such as Rh 6(CO)12(μ3-CO)4 has 86 electrons. In
some cases, it is possible to synthesize clusters in a stepwise manner. An interesting example of
this type is the buildup of a ruthenium nitride cluster; in the process of cluster building, the
nitrogen ligand is progressively encapsulated by metal atoms. These compounds are majorly
used in catalysis.

Catalysts are substances that increase the rate of a reaction but are not consumed in the reaction.
Catalysts are widely encountered in nature, industry, and the laboratory. Many of the catalysts
utilized in the chemical industry and the laboratory are organometallic compounds.

Interest in metal cluster compounds arises from unique features of their chemistry:

i. Cluster compounds provide models for studying fundamental reactions on surfaces.

ii. There is a hope that cluster compounds may provide entry to new classes of catalysts that
may be tailored to specific syntheses and may thus be more selective than existing
processes.
iii. The nature of the bonding in cluster compounds is an area wherein experiment and theory
are continuously challenging each other.
iv. The systematic synthesis of mixed metal clusters may provide for the development of
new types of supported catalysts (the discrete clusters are deposited on supports such as
alumina, silica, or zeolites).

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