TRANSITION ELEMENTS &

COORDINATION COMPOUNDS

Definition, general characteristics, oxidation states and the color (excluding the details of
electronic transitions) and calculation of spin-only magnetic moment; Coordination
compounds : Nomenclature of mononuclear coordination compounds, cis-transitions
isomerism, hybridization and geometries of mononuclear coordination compounds(linear,
tetrahedral, square planar and octahedral).

CONTENTS INTRODUCTION
 Electronic configuration The elements lying between s and p-block
 Physiochemical properties elements of the periodic table are
collectively known as transition or
 Inner transition elements
transitional elements. These elements
 Coordination compounds either in their atomic state or in any of their
 Isomerism in coordination compounds common oxidation state have partly filled
(n–1) d orbitals. n being outermost shell. In
 Hybridization and geometry of
these elements the differentiating electron
coordination compound
enters (n–1)d orbitals.
 Chelation
The name transition is given to the
elements on the basis of their position in
the P.T and their properties i.e. they
occupy a position between the highly
electropositive elements on the left and the
electronegative elements on the right. Their
properties are also intermediate of the s-
and p-block elements.
 Chemistry : Transition Elements & Coordination Compounds

1. ELECTRONIC CONFIGURATION AND IRREGULARITIES

The valence shell configurations of these elements can be represented by (n – 1)d1 –10ns 0 ,1,2 . The
observed valence shell configuration of these elements differ from their predicted configuration. The
irregularities in the observed configurations of Cr(3d 5 4s1 ), Cu(3d10 4s1 ), pd(4d10 5s 0 )
Ag(4d10 5s1 ) and Au(5d10 6s1 ) are explained on the basis of the concept that half-filled and
completely filled d-orbitals are relatively more stable than other d-orbitals. Only this factor is not
sufficient to explain the irregularities in observed electronic configuration. The net effect of all the
forces, comprising (i) nuclear electronic attraction (ii) shielding of one electron by others from other
nuclear charge (iii) inter electronic repulsion and (iv) exchange forces determines the stability of the
electronic configuration.
The configurations clearly show that strictly, According to the definition of d-block elements; Cu,
Ag and Au should be excluded from d-block elements, since these elements both in their atomic
state (with configuration (n–1) d10 ns1 ) and in their +1 oxidation state (with configuration (n–1)
d10 ), do not have partly filled (n–1) d-orbitals. Similarly Zn, Cd and Hg which both in their atomic
state [(n – 1)d10ns 2 ] and in +2 oxidation state [(n –1)d10 ] do not contain partly filled [(n–1)d]
orbitals, should also be excluded from d-block elements. Similarly is the case with Pd atom with
configuration 4d10 5s 0 . yet, in order to maintain a rational classification of elements, these elements
(viz cu, Ag, Au, Zn, Cd, Hg and Pd) are also generally studied with d-block element.

Illustration 1: The mercurous ion is written as Hg 22  while the cuprous ion is written as Cu  .

Solution: Hg 80 :[Xe]54 4f 14 5d10 6s 2

Hg  :[Xe]4f 14 5d10 6s1
In Hg I , there is one unpaired electron and we expect (mercurous) salt to be
paramagnetic. But magnetic moment of mercurous salt is zero indicating that it is
diamagnetic which is only possible when 6s electron has been used by two Hg atoms
in bonding. Hence mercurous ion is Hg 22  .

Cu 29 :[Ar] 3d10 4s1

Cu  :[Ar] 3d10
Cu I (cuprous) salt is diamagnetic by experiment and thus it is not dimeric and is thus
Cu  .

2. PHYSIOCHEMICAL PROPERTIES
The difference in the trends in the properties of d-block elements from those of s- and p-block
elements arises from a basic difference in their electronic configuration while in the building up of
elements from Li to F, the electrons are added to the outer most shell but in the case of transition
metals, the electrons are added to inner (n–1)d sub-shell. Although, the horizontal similarity
amongst the d-block elements is well marked, yet the chemistry of the elements of first transition
Chemistry : Transition Elements & Coordination Compounds

series differ considerably from that of the elements of the second and third transition series which
are more similar to each other.
Some properties of d-block elemenets
Property Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Coper Zinc
Symbol Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic No. 21 22 23 24 25 26 27 28 29 30
Atomic weight 44.956 47.90 50.942 51.996 54.938 55.847 58.933 58.710 63.54 65.37
Metallic radius 164 147 135 130 135 126 125 125 128 137
(pm)
Ionic radius 81 76, 68 74, 60 84, 69 80, 66 76, 64 74, 63 72, 62 96, 69 74
(pm)
(3+) (3+) (4+) (3+) (4+) (2+) (3+) (2+) (3+) (2+) (2+)(3+) (2+)(3+) (1+)(2+) (2+
(3+)
Covalent radius 144 132 122 118 117 117 116 115 117 125
(pm)
Boiling point (K) 3000 3533 3673 2753 2370 3273 3173 3005 2868 1180
Melting point (K) 1812 1948 2173 2163 1517 1808 1768 1726 1356 692
Density 3.0 4.5 6.11 7.2 7.44 7.86 8.86 8.90 8.92 7.13
3 –3
10  kg m
Electronegativity 1.2 1.3 1.45 1.55 1.6 1.65 1.7 1.75 1.75 1.65
(A/R)
Ionisation 1st 633 659 650 653 717 762 759 736 745 906
Energy 2nd 1235 1309 1414 1591 1509 1561 1644 1751 1958 1732
(kJ mol –1 ) 3rd 2388 2648 2866 2992 3259 2958 3230 3391 3556 3828

Electrode (III) (III) (IV) (II) (III) (II) (III) (II) (III) (II)(III) (II) (III) (II) (I) (II) (II)
Potential (V)+ –2.1 –1.2 –1.2 –0.91 –1.18 –0.44 –0.28 –0.25 + 0.52 –0.76
–1.63 –0.86 –0.74 –0.28 –0.04 + 0.4 + 0.34

2.1 ATOMIC (COVALENT) AND IONIC RADII, ATOMIC VOLUME AND DENSITY

There is a gradual decrease in atomic radius and ionic radius on moving from left to right because,
additional positive charges are placed on the nucleus and correspondingly electrons are added to the
(n–1)d orbitals. As the electrons in the d-orbitals shield the ns electrons and also themselves from
the nuclear charge incompletely, effective nuclear charge felt by them increases and hence a
contraction in size occurs. The atomic radii for the elements from Cr to Cu are very close to one
another because simultaneous addition of electron to 3d-level exercise the reverse effect by
screening the outer 4s-electrons from the inward pull of the nucleus. As a result of these two
opposing effects, the atomic radii do not alter much on moving from Cr to Cu.

As we move from alkali metals to transition elements, radii decreases steeply but within transition
elements this rate of decrease is less due to an increase in interelectronic repulsion.

The ionic radii of M2+ and M3+ ions follow the same trends as their atomic radii. The radii of M2+
ions, although somewhat smaller than that of Ca2+ ion (0.99Å) are comparable with it. Thus MO
type oxides of the transition element should be similar to CaO in many ways, although somewhat
less basic and less soluble in water. Similarly the hydration energies of M2+ ions should be similar to
 Chemistry : Transition Elements & Coordination Compounds

but somewhat greater than that of Ca2+ ion. This is borne out by facts, since the hydration energy of
Ca2+ ion is 395 kcal and the observed values of hydration energies for the elements Ti2+ … Cu2+ are
between 446 kcal and 597 kcal.

The radii of M3+ ions are slightly greater than that of Ga3+ ion (0.62Å). Thus M2O3 oxides of
transition elements should be similar to but slightly less acidic (more basic) than Ga2O3 and the
hydration energies of M3+ ions should be less than 1124 kcal which is the hydration energy of Ga3+
ion. The observed values of hydration energies for the series Sc3+ … Fe3+ are between 947 kcal and
1072 kcal.

Atomic volumes follows the same trend (decreasing) as the atomic size. While there is a general
trend of increasing density across transition series because smaller the size, the higher is the density.

2.2 METALLIC CHARACTER

All the transition elements are metals, since the number of electrons in the outer-most shell is very
small, being equal to 2. They are hard, malleable and ductile. They exhibit all the three types of
structures: face centred cubic (fcc), hexagonal close packed (hcp) and body centred cubic (bcc).
Metals of VIII and IB groups are softer and more ductile than other metals. These metals are good
conductors of heat and electricity

2.3 MELTING AND BOILING POINTS

The m.p. and b.p. of transition elements are usually high in comparison with s- and p block
elements. The m.p of elements (i.e.-transition elements) depend upon the strength of metallic bond
which increases with the availability of the unpaired d-electrons to participate in the bonding by
delocalization. In first transition series, there is a sharp decrease of m.p. after the middle (Mn having
5 unpaired electrons) in the series due to electron pairing. The softness and low m.p. of Zn, Cd and
Hg (liquid) is due to pairing of all electrons. Periodic trends in the b.p. are similar to those in m.p.

2.4 IONISATION POTENTIAL

The first ionisation potentials of transitional elements lie between the values of those of s- and p-
block elements. The first ionisation potentials of all the transition elements lie between 5 to 10
electron volts. In case of transition elements the addition of the extra electron in the (n-1) d level
provides a screening effect which shields the outer ns electrons from the inward pull of positive
nucleus on the outer ns electrons. Thus the effects of the increasing nuclear charge and the shielding
effect created due to the expansion of (n-1)d orbital oppose each other. On account of these counter
effects, the ionisation potentials increase rather slowly on moving in a period of the first transition
series.
a) First ionisation potentials : It is evident that the values for the first four 3d block elements
(Sc, Ti, V and Cr) differ only slightly from one another. Similarly the values for Fe, Co, Ni
and Cu also are fairly close to one another. The value of IEI for Zn is considerably higher. This
is due to the extra-stability of 3d10 level which is completely filled in Zn atom.
b) Second ionisation potentials : The second ionisation potentials are seen to increase more or
less regularly with the increase of atomic number. The value of IEII for Cr and Cu are higher
than those of their neighbours. This is due to the fact that the electronic configurations of Cr+
and Cu+ ions have extra stable 3d5 and 3d10 levels.
Chemistry : Transition Elements & Coordination Compounds

There is a sudden fall in the values of ionisation potentials in going from II B (Zn-group
elements) to IIIA sub-group. This sudden fall is explained on the basis that in case of IIIA
group elements the electron to be removed is from a 4p-orbital which is incompletely filled,
while in case of the II B group elements, the electron to be removed is from 4s-orbital which is
completely filled. Thus more energy will be required to remove an electron from a filled 4s-
orbital in comparison to that used to remove an electron from a 4p-orbital which is
incompletely filled.
c) Electropositive character of transitional elements as compared to that of alkali metals and
alkaline earth metals : The values of first ionisation potentials of transition elements in most
cases lie between those of s-and p-block elements. Thus the transition elements are less
electropositive than the elements of I A and II A groups. Thus, although the transitional
elements do form ionic compounds, yet they do not form ionic compounds so readily as the
alkali and alkaline earth metals do. Also, unlike the alkali and alkaline earth metals, the
transitional elements also have a tendency to form the covalent compounds under certain
conditions. Generally the compounds in which the transition elements show a smaller valency
are ionic, while those in which a higher valency is exhibited are covalent in character.

2.5 ELECTRONEGATIVITY
Transition element have fairly low values of electronegativity. It increases from Sc to Cu with a fall
at Mn and Zn. However, this increase in electronegativity is much slower because the additional
electron is being added to an inner shell which provides relatively good shielding to the outer
electrons from the nucleus. The increasing electronegativity from Sc to Cu means that the elements
become slightly less metallic and this is reflected in the increasing positive electrode potentials of
their ions M 2  and M 3 .

2.6 ELECTRODE POTENTIAL

The potential difference set up in a 1M solution of metal ions at 298 K is called standard electrode
potential against hydrogen electrode as reference.
Electrode potential is a measure of the electro positive character and it decreases along first
transition series (except Cu which has negative value) and can react with acids producing hydrogen.

2.7 OXIDATION STATES

Transition elements exhibit a wide range of oxidation states differing usually by units of one. This is
due to the fact that (n–1) d electrons may get involved along with ns electrons in bonding, as
electrons in (n–1) d orbitals are in an energy state comparable to ns electrons. There exists a general
trend of lesser number of oxidation states at each end of the series and a higher number in the
middle. The lesser number of oxidation states in the beginning of the series can be due to the
presence of too few electrons to lose or share towards the end of series it can be ascribed to the
presence of too many electrons and thus fewer empty orbitals to share electrons with the ligands.
Another feature is the reduced tendency of higher oxidation states towards the end of the series. This
could be due to steady increase in the effective nuclear charge along the series, thus not making
them readily available for bonding.
i) Minimum oxidation state. All the transition elements with the exception of Cr, cu, Ag, Au
and Hg which have a minimum oxidation state of +1 exhibit a minimum oxidation state of +2.
In most cases this +2 oxidation state arises due to the loss of two s-electrons.
 Chemistry : Transition Elements & Coordination Compounds

ii) Maximum oxidation state. Each of the elements in groups III B to VII B can show the
maximum oxidation state equal to its group number. Thus, Cr in group VIB shows a maximum
oxidation state of +6 in Cr2 O72– ion. Most of the elements in VIII group show a maximum
oxidation sate equal to +6. However, Ru and Os have a maximum oxidation state equal to +8
which is the highest oxidation state shown by any element.
iii) Relative stability of various oxidation states. The relative stabilities of various oxidation
states of 3d- series elements can be correlated with the extra stability of 3d 0 ,3d 5 and 3d10
configurations to some extent. Thus Ti 4 (3d 0 ) is more stable than Ti3 (3d1 ) and similarly
Mn 2 (3d 5 ) is more stable than Mn 4 (3d 4 ) . It may, however, be pointed out that such a
generalization for the relative stability of various oxidation states of 4d- and 5d- series elements
is often rather difficult to realise.
The higher oxidation states of 4d and 5d series elements are generally more stable than those of
the elements of 3d series, e.g., Mo, Te (4d-series elements) and W, Re (5d-series elements)
form the oxyanions: Mo VI O 42– , Tc VII O 4– , W VI O 42– , Re VII O –4 which are stable and in which the
transition elements concerned show their maximum oxidation states. The corresponding
oxyanions of Cr and Mn namely Cr VI O2– 4 and Mn
VII –
O 4 are strong oxidizing agents.
Furthermore, the highest oxidation states of second and third row elements are encountered in
compounds containing the more electronegative elements viz. F,O and Cl. Thus for the
compounds Ru VIII O 4 , Os VIII O 4 , W VI Cl6 and Pt VI F6 there are no analogs being formed by the
first row elements. The lower oxidation states particularly +2 and +3 are important in the
chemistry of aquated and complex ions of the 3d-series (i.e. first row) elements but these ions
are not very important in the chemistry of second (i.e. 4d series) and third (5d – series) row
elements. In short it may be said that in going down a sub-group the stability of the higher
oxidation states increases while that of lower oxidation states decreases.
iv) Formation of ionic and covalent compounds. Transition elements cannot form ionic
compounds in higher oxidation states because the loss of more than three electrons is prevented
by the higher attractive force exerted (on the electrons) by the nucleus. Higher oxidation states
of these metals are not formed by the actual loss of electrons but due to the formation of new
hybrid orbitals involving (n–1)d, ns and np orbitals.
The transition elements form ionic bonds in the lower oxidation states and the ionic character
of the bond decreases with the increase in the oxidation state. With this decrease in the ionic
character of the bond the basic character of the oxides decreases, e.g. MnO (oxidation state of
Mn = +2) is basic, MnO 2 (Mn  4) is amphoteric and MnO3 (Mn = +6) is acidic.

2.8 COLOUR
Compounds of transition elements are usually markedly coloured, in contrast to compounds of s-
and p-block elements which are mostly white or colourless unless the anion is coloured. As you
know, substances appear coloured when they absorb light of a particular wavelength in the visible
region of the spectrum and transmit light of other wavelengths. The colour which we see is the
colour of the transmitted wavelengths. In other words, the colour of the compound observed by us is
the complmentary colour of the colour absorbed by the compound.. You know that the transition
metals as such or in the form of ions have partly filled d-orbitals which are degenerate, i.e., they are
of equal nergy. In transition metal complexes the d-orbitals do not remain degenerate, but these split
Chemistry : Transition Elements & Coordination Compounds

into sets of orbitals of different energies. By absorbing energy, electrons can move from a d-orbital
of lower energy to that of higher energy. This transition of electron from one d-orbital to another
corresponds to a fairly small energy difference, therefore, light is absorbed in the visible region of
spectrum. For example, the aqua ion Ti(H 2 O)63 , which has one electron in the 3d orbital absorbs
light of wavelength in the yellow-green region of spectrum and therefore, appears reddish violet in
colour.
Whenever the d-orbitals are completely filled or empty, there is no possibility of electronic
transitions within the d-orbitals. In such cases, the ions will not show any colour. For example, the
compounds of Sc3 , Ti4 , Cu  and Zn 2 are white or colourless.
In the s- and p-block elements there cannot be any d-d transitions and the energy needed to promote
s or p electron to a higher level is much greater and may correspond to ultraviolet region, in which
case the compound will not appear coloured to the eye.
Relationship between colour and wavelength
Wavelength absorbed in nm Colour absorbed Colour observed
<400 UV region White/colourless
400—435 Violet Yellow-green
435—480 Indigo Yellow
480—490 Green-blue Orange
490—500 Blue-green Red
500—560 Green Purple
560—580 Yellow-green Violet
580—595 Yellow Indigo
595—605 Orange Green-blue
605—750 Red Blue-green
> 750 Infra-red White/colourless

Illustration 2: ZnO is yellow when hot, but white when cold.

Solution: Zn 2 has 3d10 E.C. hence all electrons paired thus form white salt. The Yellow
colour of hot ZnO is due to defects in the solid structure which increase with
temperature.

2.9 MAGNETIC PROPERTIES

When a substance is placed in a magnetic field of strength H, the intensity of the magnetic field in
the substance may be greater than or less than H.
If intensity > H , then substance is paramagnetic (Electrons unpaired).
If intensity < H , then substance is diamagnetic (Electrons paired).
Substances which are weakly repelled by a magnetic field are called diamagnetic, white the
substances which are weakly attracted by the magnetic field and lose their magnetism when removed
from the field are called paramagnetic. If the force of attraction is very large and the permanent
magnetization is retained, the substance is said to be ferromagnetic, e.g., iron and some iron
compounds.
It should be noted that Fe,Co and Ni are ferromagnetic. Ferromagnetic materials may be regarded as
special case of paramagnetism in which the moments of individual atoms become aligned and all
 Chemistry : Transition Elements & Coordination Compounds

point in the same direction. It is also possible to get antiferromagnetism by pairing the moments of
adjacent atoms which point in opposite directions. It occurs in salts of Fe3+, Mn2+ etc.
Paramagnetism is expressed in terms of magnetic moment, which is related to the number of
unpaired electrons as follows
  n(n  2) B.M.
n = number of unpaired electrons
B.M. = Bohr Magneton, unit of magnetic moment
More the magnetic moment more is the paramagnetic behaviour.

Illustration 3: [Co(NH3 ) 6 ]3 is diamagnetic and [CoF6 ]3– is strongly paramagnetic.

Solution: Co3

diamagnetic due to paired

[Co(NH 3 )6 ]3 electrons

d 2sp3

[CoF6 ]3–

sp3d 2

Paramagnetic due to four unpaired electrons

CO3 has 3d 6 configuration with four unpaired electrons in ground state. In presence
of NH 3 (strong ligand) all the unpaired electrons in Co3 get paired and thus
[Co(NH3 ) 6 ]3 has d 2sp 3 hybridization (octahedral structure), thus it is diamagnetic
(no electron unpaired). F – is a weak ligand hence six lone pairs of six F– are filled in
outer d-orbitals of Co 3 which has now four electrons unpaired. Thus CoF63– has
sp3d 2 hybridization in Co 3 and is thus paramagnetic due to unpaired electrons.

2.10 COMPLEX FORMATION

The chemistry of the transition metals is dominated by their tendency to form complex ions. This is
because the transition elements form small, highly charged ions which have vacant orbitals of suitable
energy to accept lone pairs of electrons donated by other groups or ligands. In case of transition
metals in high oxidation states, highly charged ions can strongly bind electrostatically a wide variety
of negative or polar ligands. In the case of transition metals in low oxidation states, the electrons in
the d orbitals become involved in  bonding with ligands. The majority of transition metal ion
complexes contain six ligands surrounding the central ion octahedrally. Some elements contain four
ligands which are either arranged tetrahedrally or less frequently at the corners of a square. Besides
these geometries, other geometries like trigonal bipyramid, pentagonal bipyramid, etc., are also
present occasionally. The bonding between the ligand and the transition metal ion can either be
predominantly electrostatic or covalent or in many cases intermediate between the two extremes.
Some of the typical complexes of the transition meals are [Fe(CN)6 ]3– ,[Ni(NH 3 ) 4 ]2 ,[Cu(CN) 4 ]3– ,
[Cu(NH3 ) 4 ]2  etc.
Chemistry : Transition Elements & Coordination Compounds

2.11 CATALYTIC PROPERTIES

Many transition metals and their compounds have catalytic properties. These metals can function as
catalysts because they can utilize both d and s electrons for the formation of bonds between reactant
molecules and the surface catalyst atoms. This increases the concentration of the reactants at the
catalyst surface and weakens the bonds in the reactant molecules with the result that the activation
energy is lowered. Compounds of transition metals are able to act as catalysts because of the case with
which the metal can adopt different oxidation states and also because of their ability to form
complexes. Some of the common catalysts used for important reactions.

TiCl3 Used as the Ziegler-Natta catalyst in the production of polythene.

V2O5 Converts SO 2 to SO3 in the contact process for making H 2SO4 .

MnO 2 Used as a catalyst to decompose KClO3 to give O2 .

Fe Promoted iron is used in the Haber-Bosch process for making NH 3 .

FeCl3 Used in the production of CCl4 from CS2 and Cl2 .

FeSO 4 and Used as Fenton’s reagent for oxidizing alcohols to aldehydes.
H 2O 2

PdCl2 Wacker process for converting C2 H 4  H 2 O  PdCl2 to CH 3CHO  2HCl  Pd

Pd Used for hydrogenation (e.g. phenol to cyclohexanone).
Pt/PtO Adams catalyst, used for reductions.
Pt Formerly used for SO 2  SO3 in the contact process for making H 2SO 4 .
Pt Is increasingly being used in three stage-convertors for cleaning car exhaust fumes.
Pt/Rh Formerly used in the Ostwald process for making HNO3 to oxidize NH 3 to NO.
Cu Is used in the direct process for manufacture of (CH 3 )2 SiCl2 used to make silicones.
Cu/V Oxidation of cyclohexanol/cyclohexanone mixtures to adipic acid which is used to make
nylon-66.
CuCl2 Deacon process of making Cl2 from HCl.
Ni Raney nickel, numerous reduction processes (e.g. manufacture of hexamethylenediamine,
production of H 2 from NH 3 , reducing anthraquinone to anthraquinol in the production of
H 2O 2 ).
Ni Reppe synthesis (polymerization of alkynes) e.g. to give benzene or cyclooctatetraene.
complexes

2.12 INTERSTITIAL COMPOUND

Transition metals can trap some small atoms like hydrogen, boron, carbon, nitrogen, etc., in vacant
spaces in their crystal lattice forming interstitial compounds. Carbon and nitrogen always occupy
octahedral holes; hydrogen is smaller and always occupies tetrahedral holes. As only transition
metals form such compounds, the d electrons are, therefore, presumably involved in the bonding.
The structure of the metal often changes during the formation of such compounds. The composition
 Chemistry : Transition Elements & Coordination Compounds

of these compounds is generally non-stoichiometric, e.g., TiH1.73 ,PdH 0.56 , but may approach regular
stoichiometry and a regular structure, e.g., TiC and VN. The later transition elements of the first
series form non-stoichiometric carbides with irregular structures, such as Cr7 C3 , which are more
reactive than the interstitial carbides of the early transition elements. These interstitial compounds
are of much importance, e.g., carbon steels are interstitial iron-carbon compounds in which the
interstitial carbon prevents the iron atoms from sliding over one another, making iron harder,
stronger but more brittle.
The presence of these atoms results in decrease in malleability and ductility of the metals but
increases their tensile strength.

3. INNER TRANSITION ELEMENTS

The elements in which the additional electrons enters (n–2)f orbitals are called inner transition
elements. The valence shell electronic configuration of these elements can be represented as
(n–2) f 0,2...14 (n – 1)d 0,1,2, ns 2 . These are also called f-block elements because the extra electron goes
to f-orbitals which belongs to (n–2)th main shell. 4f-block elements are also called lanthanides or
rare earths. Similarly 5f-block elements are called actinides or actinones. The name Lanthanides and
actinides have been given due to close resemblance with Lanthanum and actinium respectively.
Lanthanides constitutes the first inner transition series while actinides constitutes second inner
transition series.
General Characteristics:
1. Electronic Configuration
[Xe] 4f n 1 5d 0 6s 2
or [Xe] 4f n 5d1 6s 2
2. Oxidation state
They readily form M 3 ions some of them also exhibit oxidation state of +2 and +4.
3. Colouration
Ions of Lanthanides and actinides are coloured in the solid state as well as in aqueous solution
because of absorbation of light due to f–f transition since they have partly filled f-orbitals.

3.1 LANTHANIDE CONTRACTION

In lanthanides, the additional electron enters 4f-sub shell but not in the valence-shell namely sixth
shell. The shielding effect of one electron in 4f-sub-shell by another in the same sub-shell (i.e.
mutual shielding effect of 4f-electrons) is very little, being even smaller than that of d-electrons,
because the shape of f-sub shell is very much diffused. The nuclear charge (i.e. atomic number),
however, increases by unity at each step. Thus the nuclear charge increases at each step, while there
is no comparable increase in the mutual shielding effect of 4f-electrons. This results is that electrons
in the outermost shell experience increasing nuclear attraction from the growing nucleus.
Consequently the atomic and ionic radii go on decreasing as we move from La 57 to Lu 71 .

3.2 CONSEQUENCE OF LANTHANIDE CONTRACTION

1. Atomic and ionic radii of post-Lanthanide elements : The atomic radii of second row
transition elements are almost similar to those of the third row transition element because the
increase in size on moving down the group from second to third transition elements is cancelled
by the decrease in size due to lanthanide contraction.
Chemistry : Transition Elements & Coordination Compounds

2. High density of post lanthanide elements : It is because of very small size due to lanthanide
contraction.
3. Basic strength of oxides and hydroxides : Due to lanthanide contraction the decrease in size
of lanthanides ions, from La 3 to Lu 3 increases the covalent character (i.e. decreases the ionic
character) between Ln 3 and OH – ions in Ln(III) hydroxides (Fajans rules). Thus La(OH)3 is
the most basic while Lu(OH)3 is the least basic.
Similarly, there is a decrease in the basic strength of the oxides.
4. Seperation of Lanthanides : Due to the similar size (Because of lanthanide contraction) of the
lanthanides, it is difficult to separate them. But slight variation in their properties is utilized to
separate.

4. COORDINATION COMPOUNDS
4.1 INTRODUCTION
The complexes show a wide variety of physical and chemical properties which are quite different
from normal salts. These difference arise due to the difference in their structures.
Molecular or addition compounds : When solution containing two or more salts in stoichiometric
(i.e., simple molecular) proportions are allowed to evaporate, we get crystals of compounds known
as molecular or addition compounds.

KCl  MgCl2  6H 2O 
 KCl.MgCl2 .6H 2O
(carnallite)

K 2SO4  Al2 (SO 4 )3  24H 2O 

 K 2SO 4 .Al2 (SO 4 )3 .24H 2 O
(potassium alum)

CuSO 4  4NH 3  H 2O 
 CuSO4 .4NH 3 .H 2O
(tetrammin e copper(II)sulphate monohydrate)

Fe(CN) 2  4KCN 
 Fe(CN) 2 .4KCN
(potassium ferrocyanide)

These are of two types depending on their behaviour in aqueous solution.

1. Double salts or Lattice compounds : The addition compounds having the following
characteristic are called double salts or lattice compounds.
a) They exist as such in crystalline state.
b) When dissolved in water, these dissociate into ions in the same way in which the individual
components of the double salts do.
 Fe2 (aq)  2NH 4 (aq)  2SO 42– (aq)
FeSO 4 .(NH 4 ) 2 SO4 .6H 2O 
Mohr 's salt

2K  (aq) 2Al3 (aq)  4SO 42– (aq) 24H 2 O

K 2SO4 .Al2 (SO4 )3 .24H 2 O 
Potash alum

2. Coordination (or complex) compounds. It has been observed that when solutions of Fe( CN) 2
and KCN are mixed together and evaporated, potassium ferrocyanide, Fe(CN) 2 4KCN is
obtained which in aqueous solution does not give test for the Fe2 and CN – ions, but gives the
test for K  ion and ferrocyanide ion, Fe(CN) 4–
2 .
 Chemistry : Transition Elements & Coordination Compounds

Fe(CN) 2  4KCN 
 Fe(CN) 2 .4KCN 4K  Fe(CN)64–
Thus we see that in the molecular compound like Fe(CN) 2 4KCN, the individual compounds
lose their identity. Such molecular compounds are called coordination (or complex)
compounds. The difference between a double salt and a complex compound appears to be one
of the degree rather than of a more fundamental unit.
A complex compound contains a simple cation and a complex anion or a complex cation and a
simple anion or a complex cation and complex anion, e.g. K 2 [Pt IV Cl6 ], [PT IV (NH 3 ) 4 Br2 ]Br2
and [COIII (NH3 )6 ][Cr III (C2O 4 )3 ] are all complex compounds. The term complex compound is
used synonymously with the term coordination compound.
In the above complex compounds the ions, [Pt IV Cl4 ]2– ,[Pt IV (NH 3 ) 4 Br2 ]2 ,[Co III (NH3 )6 ]3
and [Cr III (C 2 O4 )3 ]3– are called complex ions. Thus a complex ion is an electrically charged
radical which is formed by the union of a metal cation with one or more neutral molecules or
anions.

4.2 IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

1. Naming of salt: If the complex is a salt, the cation is named first followed by the name of the
anion. For example, in naming K 2 [PtCl6 ] we shall name potassium first, followed by the name
of the anion. In another example of [Cu(NH3 ) 4 ]Cl2 , the name of the cation, [Cu(NH 3 )4 ]2 ,
will be placed before chloride ion.
2. For the complex entity, whether it is in cationic, anionic or neutral form, the name of the
ligand(s) is put before the name of the metal atom. However, the reverse order is followed in
writing the formula of the compound. For example, in [Cu(NH3 ) 4 ]Cl2 , we shall name the four
ammonia molecules first followed by copper and finally the presence of chloride is mentioned;
but in writing the formula copper is written before ammonia molecules.
3. Naming of the negative ligands: The names of all anionic ligands end in `o’ replacing the final
`e’ in endings. Sometimes endings are also changed. Thus the given ligands acquire the
following endings:
Ligands Endings
F– (fluoride) fluoro
–
Cl (chloride) choro
O 2– (oxide) oxo
OCN – (cyanate) cyanato
Cationic and neutral ligands have no special ending. There are a few exceptions. like `aqua’ for
H 2O , ammine for NH 3 , carbonyl for CO, and nitrosyl for NO groups.
4. Indication of the number of ligands: The number of ligands is indicated by adding prefixes
di–, tri–, tetra–, penta–, hexa–, etc. for two, three, four, five, six, etc entities of the ligand. For
example, [Co(NH3 )6 ]Cl3 will be called hexaamminecobalt chloride.
If the ligands are big complicated groups, instead of di–, tri–, tetra–, penta– prefixes we use
bis–, tris–, tetrakis–, pentakis– etc. For instance Cu(CH3COCHCOCH3 ) 2 is called
bis(acetylacetonato) copper.
Chemistry : Transition Elements & Coordination Compounds

5. Order of Naming ligands: In any complex species, the ligands are quoted in alphabetical
order, without regard to charge, before the name of the central metal atom. Numerical prefixes
indicating the number of ligands are not considered in determining that order. For example, a
compound like [CoCl(NO2 )(en)2 ]Cl will be called chlorobis (ethylenediamine) nitrocobalt(III)
chloride.
6. Oxidation state: The oxidation state of the metal ion in a complex is indicated by Roman (I),
(II), (III) etc. or an Arabic (O) and placed in parenthesis immediately after the name of the
metal. If, however, the complex species is an anion, the oxidation state of the metal is
mentioned at the end of the name of the complex.
7. Naming of complex: The name of the complex anion always ends in ‘ate’ and the Latin name
of the metal atom is used. No specific ending is used for neutral or cationic complex species.
For example, K 2 [PtCl6 ] is called potassium hexachloroplatinate(IV) and K[Ag(CN) 2 ] is
named as potassium dicyanoargentate(I).
8. A little space is given between the name of the cation and the anion. No space or hyphen is
used anywhere else.
9. Once the complex entity is completely identified according to the above rules, no mention of
the number of cations or anions used for charge balancing is required. For example,
[Co(NH3 )6 ]Cl3 is called hexaamminecobalt(III) chloride and not hexaamminecobalt(III)
trichloride. Similarly, K 2 [PtCl6 ] is named potassium hexachloroplatinate(IV) and not
dipotassium hexachloroplatinate(IV).
10. Ligands having more than one donor atom: If a ligand has more than one donor atom, the
actual atom involved in the bond formation with the metal ion is indicated by putting italicized
symbol of the atom after the name of the ligand. For example, [Ag(S2 O3 ) 2 ]3– is called
dithiosulphato s-argentate(I) ion. Some exceptions in this connection should be remembered.
These are:
–SCN thiocyanato
–NCS isothiocyanato
– NO 2 nitro
–ONO nitrite
11. Naming of Bridging ligands: A bridging group is indicated by putting the Greek letter `  ’
immediately before its name and separated by hyphens from other ligands. For example,
OH
[(H 2 O) 4 Fe  OH  Fe(H 2O) 4 ]4 is called `octaaqua-  dihydroxodiiron(III)’ ion and the
formula could be written as [(H 2O) 4 Fe(  OH) 2 Fe(H 2 O) 4 ]4 also.
12. Structural information may be given names and formulas by prefixes such as cis–, trans– etc.
[Pt(NH3 ) 2 Cl2 ] can be written as cis-dichlorodiammineplatinum(II) or trans-
dichlorodiammineplatinum(II), respectively.
Note : When writing the formula of a complex, the central atom is listed first. The coordinated
groups (i.e., ligands) are listed in the order: formally anionic ligands, neutral ligands
followed by cationic ligands. Within each group, the ligands are listed alphabetically
according to the first symbol.
Illustration 4: Write down IUPAC name of K2 [Fe(CN)3 Cl2(NH3)2]
 Chemistry : Transition Elements & Coordination Compounds

Solution: The positive part is named first followed by the negative part. In the negative part the
names are written in alphabetical order followed by metal. So the name is
Potassiumdiammnedichlorotricyano ferrate (III).
Illustration 5: Write the IUPAC name of [Co(NH3)4(NO2)2]Cl.
Solution: Here in this case the positive part is the complex. So it is name first with ligands in
alphabetical order followed by metal (but not ending in –ate as the metal belong to
the positive part of the complex. This is followed by the negative part. So the name is
Tetraamminedinitrocobalt (III) chloride.

4.3 WERNER’S THEORY OF COORDINATION COMPOUNDS

It was only in 1893, that Werner presented a theory known as Werner’ coordination theory which
could explain all the observed properties of complex compounds. More important postulates of this
theory are:
i) Most elements exhibt two types of valenceis : (a) primary valency and (b) secondary valency.
a) Primary valency. This corresponds to oxidation state of the metal ion. This is also called
principal, ionisable or ionic valency. It is satisfied by negative ions and its attachment with the
central metal ion is shown by dotted lines.
b) Secondary or auxiliary valency. It is also termed as coordination number (usually
abbreviated as CN) of the central metal ion. It is non-ionic or non-ionisable (i.e.
coordinate covalent bond type). This is satisfied by either negative ions or neutral
molecules. The ligands which satisfy the coordination number are directly attached to the
metal atom or ion and shown by thick lines. While writing down the formulae these are
placed in the coordination sphere along with the metal ion. These are directed towards
fixed position in space about the central metal ion, e.g. six ligands are arranged at the six
corners of a regular octahedron with the metal ion at its centre. This postulate predicted
the existence of different types of isomerism in coordination complexes and after 19 years
Werner actually succeeded in resolving various coordination examples into optically
active isomers.
NH3 NH3
H3 N Cl H 3N Cl
NH3 NH3
Cl Co Cl Co
NH3 NH3
H 3N Cl H2 O Cl
NH3 NH3
CoCl 3 .6NH 3 or CoCl 3 .5NH 3 H 2O or
3
III
[(Co (NH 3 )6 ] (Cl ) 3 –
[(Co III (NH 3 )5 (H 2O)]3 (Cl – )3
Chemistry : Transition Elements & Coordination Compounds

NH3 Cl
H3 N H3 N
NH 3 NH3
Cl Co Cl Cl Co
H 3N H3 N
NH 3 Cl
Cl NH3
CoCl 3 .5NH 3 or CoCl 3 .4NH 3 H 2O or
[(Co (NH 3 )5 Cl ] (Cl ) 2 [(Co III (NH 3 )4 Cl 2 ] Cl –
III 2 –

Cl
H3N
NH3
Co

Cl Cl
NH3
CoCl 3 .3NH 3 or[Co III (NH 3 ) 3 Cl 3 ]0
ii) Every element tends to satisfy both its primary and secondary vlencies. In order to meet this
requirement a negative ion may often show a dual behaviour, i.e. it may satisfy both primary
and secondary valencies since in every case the fulfillment of coordination number of the
central metal ion appears essential .
 Chemistry : Transition Elements & Coordination Compounds

Characteristic of Co(III) ammines

No. of Cl – Molar Total

ions conduc No. of
precipitate tivity ions Charge
Ammines (i.e.
d as AgCl range given by type on Ionic Formulation
complexes
(ohm –1 ) complex ions
by AgNO3
in soln.
solution
CoCl3 .6NH 3 3 430 4 (3+, 1–) [Co III (NH 3 )6 ]3 (Cl – )3

CoCl3 .5NH3 .H 2O 3 430 4 (3+, 1–) [Co III (NH 3 )5 (H 2 O)]3 (Cl– ) 2

CoCl3 .5NH3 2 250 3 (2+, 1–) [Co III (NH3 )5 Cl]2   (Cl – ) 2

CoCl3 .4NH 3 1 100 2 (1+, 1–) [Co III (NH3 ) 4 Cl2 ]  Cl –

CoCl3 .3NH3 0 0 – – [Co III (NH3 )3 Cl3 ]10

(Non. (Non-electrolyte)
electrolyt
e)

4.4 EFFECTIVE ATOMIC NUMBERS

The number of secondary valencies in the Werner’s theory is now called the coordination number of
the central metal in the complex. This is the number of ligand atoms bonded to the central metal ion.
Each ligand donates an electron pair to the metal ion, thus forming a coordinate bond. Transition
metals form coordination compounds very readily because they have vacant d orbitals which can
accommodate these electron pairs. The electronic arrangement of the noble gases is known to be
very stable. Sidgwick, with his effective atomic number rule, suggested that electron pairs from
ligands were added until the central metal was surrounded by the same number of electrons as the
next noble gas. Consider potassium hexacyanoferrate(II) K 4 [Fe(CN) 6 ] (formerly called potassium
ferrocyanide). An iron atom has 26 electrons, and so the central metal ion Fe2 has 24 electrons.
The next noble gas Kr has 36 electrons. Thus the addition of six electron pairs from six CN – ligands
adds 12 electtrons, thus raising the effective atomic number (EAN) of Fe2 in the complex
[Fe(CN)6 ]4– to 36.
[24  (6  2)  36]
The EAN rule correctly predicts the number of ligands in many complexes. There are, however, a
significant number of exceptions where the EAN is not quite that of a noble gas. If the original metal
ion has an odd number of electrons, for example, the adding of electron pairs cannot result in a noble
gas structure. The tendency to attain a noble gas configuration is a significant factor but not a
necessary condition for complex formation. It is also necessary to produce a symmetrical structure
(tetrahedral, square planar, octahedral) ireespective of the number of electrons involved.
Chemistry : Transition Elements & Coordination Compounds

Effective atomic numbers of some metals in complexes

Electrons Electrons
Atomic
Atom Complex lost in ion gained by EAN
number
formation coordination
Cr 24 [Cr(CO)6 ] 0 12 36
Fe 26 [Fe(CN)6 ]4– 2 12 36
Fe 26 [Fe(CO)5 ] 0 10 36
[Kr]
Co 27 [Co(NH3 ) 6 ]3 3 12 36
Ni 28 [Ni(CO) 4 ] 0 8 36
Cu 29 [Cu(CN) 4 ] 3– 1 8 36
Pd 46 [Pd(NH 3 )6 ]4 4 12 54 [Xe]
Pt 78 [Pt(Cl6 ]2– 4 12 86 [Rn]
Fe 26 Fe(CN)6 ]3– 3 12 35
Ni 28 [Ni(NH 3 )6 ]2  2 12 38
Pd 46 [PdCl 4 ]2– 2 8 52
Pt 78 [Pt(NH3 ) 4 ]2  2 8 84

4.5 SHAPES OF d ORBITALS

Since d orbitals are often used in coordination complexes it is important to study their shapes and
distribution in space. The five d orbitals are not identical and the orbitals may be divided into two
sets. The three t 2g orbitals have identical shape and point between the axes, x, y and z. The two eg
orbitals have different shapes and point along the axes. Alternative names for t 2g and eg are d and
d respectively.
x x y

t 2g
orbitals y z z
(d)

d xy d xz d yz

x z

eg
orbitals y
(d )

d x 2 – y2 d z2
 Chemistry : Transition Elements & Coordination Compounds

5. ISOMERISM
Compounds that have the same chemical formula but different structural arrangement are called
isomers. Because of the complicated formula of many coordination compounds,the variety of bond
types and the no of shapes possible, many different types of isomerism occur.
[A] STRUCTURAL ISOMERSIM
(I) Polymerization Isomerism : This is not true isomerism because it occurs between
compounds having the same empirical formula, but different molecular weights. For example,
[Pt(NH3 )2Cl2], [Pt(NH3)4 ][PtCl4], [Pt(NH3)4] [Pt(NH3 )Cl3]2.
(II) Ionization Isomerism : This type of isomerism is due to the exchange of groups between the
complex ion and the ions outside it. [Co(NH3)5Br]SO4 is red – violet. An aqueous solution
gives a white precipitate of BaSO4 with BaCl2 solution, thus confirming the presence of free
SO 24 ions. In contrast [Co(NH3)5SO4 ]Br is red. A solution of this complex does not give a
positive sulphate test with BaCl2. It does give a cream – coloured precipitate of AgBr with
AgNO3, thus confirming the presence of free Br– ions.
(III) Hydrate Isomerism : Three isomers of CrCl3.6H2 O are known. From conductivity
measurements and quantitative precipitation of the ionized chlorine, they have been given the
following formulae:
[Cr(H2O)6]Cl3 violet (three ionic chlorines)
[Cr(H2O)5Cl]Cl2.H2O green (two ionic chlorines)
[Cr(H2O)4Cl2].Cl.2H2O dark green (one ionic chlorine)
(IV) Linkage Isomerism : Certain ligands contain more than one atom which could donate an
electron pair. In the NO 2 ion, either N or O atoms could act as the electron pair donor. Thus
there is the possibility of isomerism. Two different complexes [Co(NH3)5NO2]Cl2 have been
prepared, each containing the NO 2 group in the complex ion.
(V) Coordination Isomerism : If the complex is a salt having both cation and anion as complex
ions then the ligands can exchange position between the cation and the anion. This will result
in the formation of coordination isomers. For example
[Co(en)3 ][Cr(C 2O 4 )3 ] and [Co(en) 2 (C 2 O4 )][Cr(en)(C 2 O4 ) 2 ]
[Cr(en) 2 (C2 O4 )][Co(en)(C 2 O4 ) 2 and [Cr(en)3 ][Co(C 2O 4 )3 ]
(VI) Coordination Position Isomerism : If in a multinuclear complex the distribution of ligands
around the metal centres changes it will result in a different isomer. Such an isomerism is
called coordination position isomerism. Some typical examples are :
NH 2 NH 2
[(NH 3 ) 4 Co   Co(NH 3 ) 2 Cl 2 ] Cl2 and [Cl(NH 3 )3 Co   Co(NH3 ) 3 Cl]Cl2
O2 O2
Cl Cl
[(R 3P) 2 Pt   PtCl 2 ] and [Cl(R 3P) Pt   Pt(R 3P)Cl]
Cl Cl
(VII) Electronic Isomerism: The complex [Co(NH3 )5 NO]Cl2 exists in two forms. One is black
paramagnetic while the other is pink and diamagnetic. Thorough structural studies show that
the black isomer is a Co(II) complex containing neutral NO group whereas the pink one is a
Co(III) complex where NO – ion is present. This kind of isomerism is known as electronic
isomerism.
[B] STEREO ISOMERISMS
Chemistry : Transition Elements & Coordination Compounds

Stereoisomers have the same bonds but the arrangement of atoms in space is different.
Stereoisomerism can be divided into two kinds: geometrical and optical.
(I) Geometrical isomerism or cis-trans isomerisms: It occurs when ligands can assume
different positions around rigid bonds with the metal ion. For example, the compound
Pt(NH3 ) 2 Cl2 has a square planar structure. The two possible arrangements are.

H3N Cl H3 N Cl

Pt Pt

H3N Cl Cl NH3

In the cis-isomer the two ammonia molecules are next (cis) or adjacent to each other whereas
in the trans-isomer the two ammonia molecules are across (trans) to each other. This type of
isomerism is not possible for complexes with coordination number 2 (linear molecule), 3
(trigonal planar) and 4 (tetrahedral geometry).
For square planar complexes Ma 4 ,Ma 3b or Mab3 where a and b etc., are monodentate
ligands, again the geometrical isomerism is not possible. However, square planar complexes
of the type Ma 2 b 2 , Ma 2 bc, Mabcd and M(AA)2 , M(AB) 2 where AA and AB represent
symmetrical and unsymmetrical chelating agents – do give geometrical isomers. A few
examples are given below:

Type Compound Isomers

Ma 2 b 2 Pt(NH3 ) 2 Cl2 H3 N Cl H3 N Cl

Pt Pt
H3 N Cl Cl NH 3

Ma 2 bc P t(NH 3 ) 2 ClBr H3 N Cl H3N Cl

Pt Pt
H3N Br Br NH 3

Mabcd Pt(NH 3 )(C5 H5 N)(Cl)(Br)

H3 N NC5 H5 H3N NC5 H 5 Cl

H3 N
Pt Pt Pt
Br Cl Cl Br Br NC5 H5
 Chemistry : Transition Elements & Coordination Compounds

Bridged binuclear planar complexes like Pt[(PEt 3 )Cl2 ]2 may exist in three isomeric forms:
Et 3P Cl Cl Et 3P Cl PEt 3 Et 3P Cl Cl
Pt Pt Pt Pt Pt Pt
Cl Cl PEt 3 Cl Cl Cl Et 3P Cl Cl
trans– cis– unsymmetrical

Six coordinated octahedral complexes of the type Ma 4 b 2 , Ma 3b3 , Ma 3 b 2c, Ma 3 bcd, Ma 2 b 2 cd ,

Ma 2 bcde, Mabcdef would all give geometrical isomers. Systems with one or two bidentate ligands
and rest monodentate would also give geometrical isomers. Thus we see that with this geometry a
lage number of isomers are possible whether they can be isolated or separated is a different question
which depends on so many factors. As we increase the number of different ligands, the possible
number of isomers increases. For example, Ma 4 b 2 type of complex would give only two isomers
cis–and trans–. Similarly for Ma 3b 3 type of complex we again get two isomers facial (fac–) and
meridional (mer–) isomers. In the former (fac–) three ligands of one type form one triangular face of
the octahedron and the other three on the opposite face. In the latter (mer–) one set of these ligands
are arranged around an edge of the octahedron whereas the other set occupies the opposite edge as
shown in figure.
a a

a b b b

M M
a b b a

b a

Facial and meridional isomers of Ma 3b 3 complex

(II) Optical isomerism: Two isomers which have almost identical physical and chemical
properties like mp, bp, density, colour etc., but differ in the way they rotate the plane-
polarised light are called optical isomers. Such optically active compounds exist in pairs and
are known as stereoisomers or enantiomers. These isomers aer non-superimposable mirror
images of each other. Hence, any molecule which contains either a centre of symmetry or a
plane of symmetry will not show optical isomerism.
Optical isomerism is rarely observed in square planar complexes. Tetrahedral complexes of the type
[M(AB) 2 ] do give optical isomers as shown in figure especially where M = Be, B etc.
A A

A A
M M

B B B B
However, optical isomerism is very common with octahedral complexes of the type
M(AA)3 ,M(AA) 2 ab, M(AA)a 2 b 2 , M(AA)(BB)a 2 etc. A few typical examples are shown in
figure.
Chemistry : Transition Elements & Coordination Compounds

3 3
CH 2 CH 2

CH 2 CH 2
H2 N H2 N

H2N NH2 H2N NH 2

H 2C Co Co H 2C
NH 2 H2N
H 2C H2N NH2 H 2C

H2N CH 2 CH2 NH2

CH2 CH 2

 
N N
en en

NO2 O2 N
N N
Co Co

N NO2 O2 N N
en en
N N

Illustration 6: How do you distinguish between the following pairs of isomers?

i) [Cr(NH3 )5 Br]Cl and [Cr(NH 3 )5 Cl]Br
ii) [Co(NH3 )6 ] [Cr(NO 2 )6 ] and [Cr(NH 3 )6 ][Co(NO 2 )6 ]
Solution: i) The isomers can be distinguished by using AgNO3 reagent. One gives curdy
precipitate of AgCl soluble in ammonia while the other will form light yellow
precipitate of AgBr partly soluble in ammonia.
ii) The isomers can be distinguished by passing their aq. solutions through a
cation exchanger. In the isomer [Co(NH3 )6 ][(Cr[NO 2 )6 ] the cation
[Co(NH3 ) 6 ]3  will be replaced by H  ions from the resin. The resulting
solution will thus contain H 3[Cr(NO 2 )6 ] . In the other case, the resulting
solution after passage through the exchanger will contain H 3 [Co(NO 2 )6 ] . On
adding KCl solution, [Co(NO 2 )6 ]3– ion will give yellow precipitate of
potassium cobaltinitrate, K 3 [Co(NO 2 )6 ] . Hence the resulting solutions
obtained from the two isomers can be distinguished.

6. HYBRIDIZATION AND GEOMETRY

6.1 FORMATION OF AN OCTAHEDRAL COMPLEX
Let us consider the case of six ligands forming an octahedral complex. For convenience, we may
regard the ligands as being symmetrically positioned along the axes of a Cartesian co-ordinate
system with the metal ion at the origin. To simplify the situation, we can consider an octahedral
complex as a cube, having the metal ion at the centre of the body and the 6 ligands at the face
centres.
 Chemistry : Transition Elements & Coordination Compounds

and if we take the metal ion as the origin of a Cartesian co-ordinate, the ligands will be along the
axes. As in the case of a spherical field, all of the d-orbitals will be raised in energy relative to the
free ion because of negative charge repulsions. However it should be pictorially obvious that not all
of the orbitals will be affected to the same extent. The orbitals lying along the axes
d z2
and d x 2  y2  will be more strongly repelled than the orbitals with lobes directed between the
axes (dxy, dxz, dyz). The d-orbitals are thus split into two sets with the d z2 and d x 2 – y 2 at a higher
energy than the other three.
d z2
,d
x2  y 2

0

dxy, dyz, dxz

[A] Factors affecting the magnitude of 0

i) Oxidation state of the metal ion: The magnitude of 0 increases with increasing ionic charge
on the central metal ion. As the ionic charge on the metal ion increases greater is the attraction
for the ligands, greater the repulsion and hence greater the magnitude of 0.
ii) Nature of the ligands: Based on experimental observation for a wide variety of complexes, it
is possible to list ligands in order of increasing field strength in a spectrochemical series.
Although it is not possible to form a complete series of all ligands with a single metal ion, it is
possible to construct one from overlapping sequences, each constituting a portion of the series:
I–  Br–  S2–  SCN–  Cl–  N3–, F–  urea, OH–  ox, O2–, H2O  NCS–  py, NH3
 en  bpy, phen  NO2–  C6H5–  CN–  CO.

The spectrochemical series and other trends described allow one to rationalise differences in
spectra and permit some predictabiltiy. If the splitting of the d-orbitals resulted simply from the
effect of point charges (ions (or) dipoles), one should expect that anionic ligands would exert the
greatest effect. To the contrary most anionic ligands lie at the low end of the spectrochemical
series. Further more, OH– lies below the neutral H2O molecule and NH3 produces a greater
splitting than H2O. Despite its imperfections, the basic theory can be used to interpret a number of
effects in co-ordination chemistry.

[B] Outer orbital and Inner orbital complexes

Consider the complexes [CoF6]3– and [Co(NH3)6 ]3+
The electronic configuration of Co3+ ion is
Chemistry : Transition Elements & Coordination Compounds

3d 4s 4p 4d

↿⇂ ↿ ↿ ↿ ↿
In a weak ligand field such as [CoF6 ]3–, the approach of the ligand causes only a small split in the
energy level.

Since the ligand is a weak field ligand, its repulsions with the
electrons in d z 2 and d x 2  y2 orbitals are very less (or) in other words
we can say that the electrons in d z2 and d x 2  y 2 cannot move away
from the approaching ligands since they have insufficient energy to
pair up with the electrons in dxy, dyz and dxz orbitals.

Thus there are no vacant orbitals in the 3d shell and the ligands occupy the first six vacant orbitals
(one 4s, three 4p and two 4d). Since outer d orbitals are used, this is an outer orbit complex. The
orbitals are hybridised and are written sp3d2 to denote this. Since none of the electrons has been
forced to pair off, this is a high spin complex and will be strongly paramagnetic because it contains 4
unpaired 3d electrons.

Under the influence of a strong ligand field as in the complex [Co(NH3)6]3+, the approach of the
ligand causes a greater split in the energy level.

Since, the split is very high, we can say that the energy difference
between the two sets of orbitals is much greater and this energy
difference is sufficient to allow the electrons in d z 2 and d x 2  y2
orbitals to move into the half filled dxz, dxy and dyz orbitals, even
though this pairing requires energy. We can also view this like, the
ligand repel the electrons in higher energy level to an extent such
that they get paired up against Hund's rule

So,

The d z2 and d x 2  y 2 orbitals become vacant.

The six ligands each donate a lone pair to the
first six vacant orbitals, which are: two 3d, one
4s and three 4p. Inner d-orbitals are used and
so this is an inner orbital complex. The orbital
are hybridised and written d2sp3 to denote the
use of inner orbitals.

Since, the orginal unpaired electrons have been forced to pair off, there is a low spin complex and is in
fact diamagnetic.
 Chemistry : Transition Elements & Coordination Compounds

The inner and outer orbital complexes may be distinguished by magnetic measurements. Since the outer
orbital complexes use high energy levels, they tend to be more reactive. The inner orbitals are sometimes
called inert orbitals.

Distribution of d-electrons in t 2g and eg sets in strong(er)

and weak (er) octahedral ligand fields.

Strong(er) field (low-spin or spin-paired Weak(er) field (high-spin or spin free

Ions
complexes) ( 0  P) complexes) ( 0  P)

t p2g egq t p2g egq

n s n S
Configuration configuration

t12g eg0 t12g eg0

d1 1 ½ 1 ½
d2 t 22g eg0 2 1 t 22g eg0 2 1
d3 t 32g eg0 3 3/2 t 32g eg0 3 3/2

t 42g eg0 t 32g e1g

d4 2 1 4 2
d5 t 52g eg0 1 ½ t 32g eg2 5 5/2
d6 t 62g eg0 0 0 t 42g eg2 4 2

d7 t 62g e1g 1 1/2 t 52g eg2 3 3/2

t 62g eg2 t 62g eg2

d8 2 1 2 1
d9 t 62g eg3 1 ½ t 62g eg3 1 ½
d10 t 62g eg4 0 0 t 62g eg4 0 0

6.2 FORMATION OF A SQUARE PLANAR COMPLEX

If the central metal ion has eight d-electrons, these will be arranged as
↿⇂ ↿⇂ ↿⇂ ↿ ↿
In a weak octahedral ligand field, a regular octahedral complex is thus formed by using outer d-
orbitals.
However, under the influence of a strong ligand field, the electrons in the d z2 and d x 2  y2 orbitals
may pair up, leaving one vacant d-orbital, which can accept a lone pair from a ligand.
For example consider [Ni(CN)4]2–
Chemistry : Transition Elements & Coordination Compounds

The electronic configuration of Ni2+ ion is

3d 4s 4p

X ↿⇂ ↿⇂ ↿ ↿

Consider, a Ni2+ ion with one electron in the d x 2  y2 orbital and one
in the d z2 orbital. The approach of ligands along x, y and z axes
will result in increase in the energy of these orbitals. Because the
d x 2  y2 orbital is attacked by four ligands and the d z2 by only two,
the energy of d x2  y2 orbital will increase most. If the ligands have
enough strong field, the electrons will be forced out of the
d x2  y2 orbital into the d z2 .

Thus four ligands can approach along x, –x, y and –y axes. A ligand approaching in the z (or) – z
direction attempting to donate a lone pair meets the very strong repulsive forces from a completely
filled d Z2 orbital. Thus only four ligands succeed in bonding to the metal.

6.3 FORMATION OF TETRAHEDRAL COMPLEXES

A regular tetrahedron is related to a cube with an atom at the centre and four of the eight corners
occupied by ligands.
z

x
y

The directions x,y and z point to the centre of the faces. The d Z2 and d x2  y2 orbitals point along x,y
and z axis and dxy, dyz and dxz orbitals point in between x,y and z.
The directions of approach of the ligands does not coincide exactly with either the d z2 and d x 2  y 2
orbitals (or) the dxy, dyz and dxz orbitals. The approach of ligands raises the energy of both sets of
orbitals, but since the dxy,dyz and dxz orbitals correspond more closely to the position of the ligands,
their energy increases most and the d Z2 and d x 2  y 2 orbitals are filled first. This is opposite to what
happens in octahedral complexes.
Consider, the complex ion, [FeCl4]–. The electronic configuration of Fe3+ ion is
3d 4s 4p

↿ ↿ ↿ ↿ ↿

Since Cl– ion is a weak field ligand it is unable to pair the unpaired electrons and hence, the Cl– ion
uses 4s and 4p orbitals to form a tetrahedral complex of sp3 hybridisation.

7. CHELATION
Polydentate ligands whose structures permit the attachment of their two or more donor atoms (or
sites) to the same metal ion simultaneously and thus produce one or more rings are called chelate or
 Chemistry : Transition Elements & Coordination Compounds

chelating ligands (from the Greek for claw) or chelating groups. However, it should be noted that
every multidentate ligand is not necessarily a chelating ligand — the coordinating atoms of the
ligand may be so arranged that they cannot be coordinated to the same metal atom to produce a ring
structure. Thus NH 2 — CH 2 — CH 2 — NH 2 is a chelating ligand, while

—(CH 2 ) 2 —
N — CH 2 — CH 2 — NH 2

—(CH 2 ) 2 —
is not, although both are diamines. The formation of such rings is termed chelation and the resulting
ring structures have been called chelate rings or simply chelates by Morgan and Drew. These are
also called chelated complexes or cyclic complexes and the term chelation is also called cyclisation.
7.1 CLASSIFICATION OF CHELATES
Since the polydentate ligands may be attached to the central metal ion through two kinds of
functional groups namely acidic and coordinating groups to form covalent and coordinate linkages
respectively, the classification of chelates follows the number and kind of linkages by which the
metal ion is attached with the ligands. The covalent bonds are formed by the replacement of one or
more H-atoms from the acidic groups present in the ligand by the metal atom. The examples of most
common grops of this type are —COOH (carboxyl), —SO 3 H (sulphonic), —OH (enolic hydroxyl)
and =NOH (oxime). Coorinating linkages, without the replacement of H, are formed by the donation
of an electron pair from the ligands. The examples of most common groups of this type are — NH 2
(primary, secondary and tertiary amines), = NOH (oxime), —OH (alcoholic hydroxyl), = CO
(carbonyl) and —S— (thio ether).
Ordianrily such chelate rings as mentioned above are most stable, because of reduced strain, when they have 5
or 6 members including the metal ion. The enhanced stability of complexes containing chelated ligands (i.e.,
multidentate ligands) is known as the chelate effect.