XII –CHEMISTRY

Ch-9 COORDINATION COMPOUNDS

LIJI. ELIZABETH
 REVISED SYLLABUS
• Coordination compounds - Introduction, ligands, coordination
number, colour, magnetic properties and shapes, IUPAC
nomenclature of mononuclear coordination compounds.
Bonding, Werner's theory, VBT, and CFT.
 Coordination compounds and complex ions

• Coordination compounds are the compounds in which the central

metal atom is linked to a number of ions or neutral molecules by
coordination bonds ,i.e donation of lone pair of electrons by
these ions or neutral molecules to the central metal atom
• Ex: Nickel tetracarbonyl , Ni(CO)4 in which molecules are linked
to the central Nickel atom by co-ordinate bonds by donating lone
pairs of electrons is a coordination compound.
 Difference between a double salt and a complex

• Double salts dissociate into simple ions completely when dissolved in water.
• Ex: KCl.MgCl2.6H2O ----K+ +Mg2+ +3Cl- + 6H2O.
• On the other hand ,in complexes the complex ion almost does not dissociate.
• Ex: K4[Fe(CN)6 ] dissociates to give K+and [ Fe(CN)6 ]4- ions in the aqueous
solution. The solution does not give the tests of Fe2+& CN- ions because
the complex ion, [Fe(CN)6]4- does not dissociate into Fe 2+ & CN- ions.
• K4[Fe(CN)6]---- 4K+ [Fe(CN)6]4----doesn‘t ionize to give Fe2+& CN- ions .
 Complex ion
• If the species formed by linking of a number of Ions or
molecules by co-ordinate bonds to the central metal atom
carries positive or negative charge it is called a complex Ion .
• Ex; [Fe(CN)6]4-, [Cu(NH4)4]2+, [Ag(CN)]-
• Hence coordination compounds may also be defined as those
compounds which contain Complex ions
• .Ex : K4[Fe(CN)6], Na[Ag(CN)2]etc. That is why coordination
compounds are also called complexes.
 Types of complexes
• There are following three types of complexes
• 1. A complex in which Complex ion carries a net positive charge is
called cationic complex Ex: [Co(NH3)6]3+, [Ni(NH3)6]2+, etc.
• 2. A complex in which the complex ion carries a net negative
charge is called anionic complex. Ex:[Ag(CN)]- , [Fe(CN)6]4- etc.
• 3. A complex carrying no net charge is called a neutral complex or
simply a complex.Ex : [Ni(CO)4], [Co(NH3)Cl3]etc.
Important terms used in coordination
compounds
• Ligands & central metal atom / ion
• The donor atoms ,molecules or anions which donate a pair of
electrons to the metal atom or ion and form a co-ordinate
bond with it are called Ligands .
• The metal atom or ion to which these ligands are attached is
called Central metal atom or ion.
• The ligand may contain one or more than one atom .If only one atom is present in
its molecule which can co-ordinate , then it is called a unidentate This is also
referred to as a monodentate.When a ligand can bind through two donor atoms as
in H2NCH2CH2NH2(ethane-1,2 diamine) or C2O4 2- (oxalate), the ligand is said to
be didentate and several donor atoms are present in a single ligand as in
N(CH2CH2NH2)3 , the ligand is said to be poly dentate.
• Example:
Ethylenediaminetetraacetate ion (EDTA 4-) is an important hexadentate
ligand. It can bind through two nitrogen and four oxygen atoms to a
central metal ion.
Structure of di dentate &hexadentate ligands

Ethane 1,2 diammine

Structure of ethane I,2 – diamine(en)
 Denticity and chelation :
• Denticity of a ligand : The number of donor atoms or group from a given ligand
attached to the same central metal atom is known as the denticity of the ligand.

• Chelating ligands:

• The ligand may contain two donor atoms positioned in such a way that a five or
six membered ring is formed within the metal atom, then it is called bidentate or
didentate chelating ligand and ring is called chelate ring, the complex is called a
metal chelate & this property is called a chelation.
Ambidentate ligands
Unidentate ligands containing more than one coordinating atoms
are called and ambidentate ligands.

Ex: Nitrito-N , Nitrito-O

O M O N O
M N
O
Thiocyanato, isothiocyanato
M SCN M NCS
 Coordination number:

• The coordination Number: It may be defined as the number of atoms

of the ligands which are directly bonded to the central Metal atom or
Ion .
• Or coordination number may be defined as the number of co-
ordinate bonds formed with the central metal atom by the ligands.
• Ex:[Ag(CN)2] - , [Cu(NH3) 4] 2+ - the coordination number of Ag &
Cu are 2, 4 respectively.
• Ex: [Fe(C2O4)3]3- the co ordination number of Fe is 6 because
C2O4. 2- is a didentate ligand .
• Note: The coordination number of the central atom ion is determined
only by the number of Sigma bonds formed by the ligand with the
central atom not pi bond.
 Coordination sphere ,coordination entity & counter ion
The central atom and the ligands which are directly attached to it are
enclosed in a square bracket and are collectively termed as the
coordination sphere or coordination entity.

The ligands and the metal atom inside the square bracket behave as a
single constituent unit .The ionizable groups are written outside the
bracket and are called counter ions.

Ex : [Cu(NH3)4)] SO4, the complex ion , [Cu(NH3)4]2+, in which Cu2+is

the central metal ion & 4 - NH3 molecules are ligands , forms the
coordination sphere and SO4 2- ions are the counter ions.
 Coordination polyhedron
• The spatial arrangement of the ligand atoms which are directly
attached to the central atom/ ion is called a coordination polyhedron
around the central atom/ ion.
• The most common Coordination polyhedra are tetrahedral , square
planar ,octahedral ,square pyramidal and trigonal pyramidal.
• [Co(NH3)6] 3+-- octahedral
• [-Ni(CO)4] - tetrahedral
• [PtCl4]2--- square planar.
Oxidation number of central atom
• The oxidation number of the central atom is defined as the charge that it
carries as calculated by assigning appropriate charges to the ligands
and equating the sum of the charges on the central atom and the ligands
• equal to charge on the coordination sphere.
• Ex : Fe in Fe[(CN)6]3- is +3 but the coordination number is 6 .
• Ni in [Ni(CO)4] is zero , as CO carries no charge,
• It is represented by Roman numbers I,II,III etc.in the parenthesis after the
name of the central atom.
Examples
• 1. What is the oxidation number of Cu in [ Cu (NH3)4 ] SO4?
Since the complex is neutral, X + 0 x 4 + (-2) =0 ; X= +2

2. What is the oxidation number of Fe in [Fe(CN)6] 4- ?

As each CN- ion carries charge = -1, charge on 6 CN- ions = -6. As total
charge on the complex ion =-4 , therefore , charge on Fe must be = +2 , i.e
oxidation number of Fe = +2 . We write it as Fe (II) .
Homoleptic and Heteroleptic complexes

Complexes in which the metal atom or ion is linked to only one type
of ligands are called homoleptic complexes.
Ex: [Co(NH3)6 ]3+
The complexes in which the metal atom or ion is linked to more
than one kind of ligands are called heteroleptic complexes
Ex: [Co(NH3)4Cl2]+.
 Rules for naming of mononuclear coordination compounds

1.Order of naming ions: The positive ion (cation ) whether simple

or complex , is named first followed by negative ion (anion). The
name is started with a small letter & the complex part is written as
one word .
Ex: [Co(NH3)6]Cl3 , hexaamminecobalt (III) chloride
K2[ PtCl6] , potassiumhexachloro platinate(IV)
But the non – ionic & molecular complexes are given one word
name
EX:[Co(NH3)(NO2)3] –triamminetrinitrocobalt(III)
[Pt(NH3)2Cl4] ---diamminetetrachloroplatinum(IV)
2.Naming of ligands:
i)Negative ligands end in –o
Ex: CN- (cyano), Cl- (chloro), Br- (bromo), F- (fluoro),
NO2- (nitro ),OH- (hydroxo) , O2- (oxo), H- (hydrido)
*Note:
If the name of the anionic ligand ends in ide, ite, or ate, the last
‘ e’ is replaced by ‘ o ’ giving – ido , ito , ato respectively.
Ex: SO4 2-  sulphato; C2O4 2- oxalato ; NH2 -  amido;
ONO-  nitrito ; NO3 -  nitrato ; SCN- thiocyanato ;
NCS- isothiocyanato .
ii) Neutral ligands have no special ending
Ex: NH3 (ammine) ; H2O (aqua) ; CO (carbonyl ) ; CS
(thiocarbonyl) , NO (nitrosyl)
iii) Positive ligands – end in -ium ,
Ex :NH2-NH3 + (hydrazinium) ; NO+ (nitrosonium) ; NO2+
(nitronium).
:
 Rules for writing of mononuclear coordination
compounds
1.Formula of the cation whether simple or complex is written first
followed by that of anion .
2.The entire coordination entity whether charged or not is written in
square brackets.
3.Within the coordination sphere/entity ,the symbol of metal is
written first followed by the ligands which to be written
alphabetically.
Ex: [ Co (NH3)4 (H2O) (Cl)] Cl2
( alphabetically arranged)
• 4.The formulas of the poly atomic ligands are enclosed in parentheses.
Abbreviations used for the ligands, for example , en ( ethane1,2
diamine) etc are also enclosed in parentheses.

• 5.The metal atom as well as all ligands are listed without any space
between them.
• 6.If the formula of only the complex ion , the charge on the complex ion
is indicated outside the square bracket as right superscript with the
number before the sign .
• Ex: [Fe (CN)6 ]3- ;
[Cu (NH3)4 ]2+
• 7.The no: of cations or anions to be written in the formula is calculated on
the basis that total positive charge must be equal to the total charge, as the
complex as a whole is electrically neutral.
 Write IUPAC name of the following
compounds
• 1.[Co(NH3)5Cl]Cl2
• pentaamminechloridocobalt(III) chloride
2.[Co(en)2Cl (ONO)]+
• Chloridobis (ethane1,2 – diamine )nitrito cobalt(III)ion.
3.[Cr(NH3)6]3+
Hexaamminechromium(III)ion
• Name the complexes
• 4.K2[Cu(CN)4]
• potassium tetracyanocuprate(II)

• 5.[Mn(H2O)6]2+
• hexaaquamanganese(II)ion
• 6.[Co(NH3)5Cl]Cl2
• Pentaamminechlridocobalt(III) chloride.
• 7.[Co(CN)6]3-
• hexacyanocobaltate(III)ion.
• 8.[Ni(CN)4]2-
• tetracyanonickelate(II)ion.
• 9.Li[AlH4]
• lithiumtetrahydridoaluminate(III).
• 10.K3[Fe(C2O4)3
• potassiumtrioxalatoferrate(III).
Bonding in coordination compounds
Werner’s theory of coordination compounds
As per Werner ‘ theory of coordination compounds- ,
Metals possess two types of Valencies called
1. primary or principal or ionisable valency
2. secondary or non ionisable valency
• Example : CoCl3. 6 NH3
• As per Alfred Werner’s conclusions, to the mixture of cobalt
chloride & ammonia solution when AgNO3 solution is added
, it was observed all chloride ions were precipitated as AgCl
in the first compound but in other cases some chloride ions
were precipitated but other remained in the solution.

• The conductivities from the solution of the obtained

compounds were also found to be different showing that the
number of ions produced in the solution from these
compounds were not same.
• Examples Based on Postulates of Werner's Theory

• CoCl3.(NH3)6
• Cobalt has a primary valency (oxidation state) of three and
exhibits secondary valency (coordination number) of 6. We
represent the secondary valencies by thick lines and the
primary valency by broken lines.
• Primary Valency :These valencies are those which a metal
exhibit in the formation of it’s simple salts
• EX: In the formation of Pt Cl4 , CoCl3 , CuSO4 , AgCl the
primary valencies of Pt ,Co, Cu, Ag are 4, 3, 2 &1 respectively.
• Secondary valency: These valencies are those which a metal
atom or cation exercises towards neutral molecules or
negative groups ( ligands) in the formation of its complex
ions .
• Every metal cation has a fixed the number of secondary
valencies. The secondary valency is also termed as the
coordination number.
• In [Pt( NH3)6]Cl4, -_ 6 for Pt 4+
• [Co(NH3)6]Cl3. -- 6 for Co3+
• [Ag(NH3)2]Cl. ---2 for Ag+

• 3. Every metal has a tendency to satisfy both it’s primary &

secondary Valencies . Primary valencies are satisfied by
negative ions whereas secondary valency are satisfied by
negative ions or neutral molecules (ligands).
• 4. The ligands satisfying secondary valencies are always
directed towards fixed positions in space there by giving a
definite geometry to the complex but the primary valencies
are non –directional.

• Ex: The six such secondary valencies were regarded as

directed to the spices of a regular octahedral circumscribed
about the metal ion whereas four such bonds might be
arranged either in a square planar or tetrahedral manner..
Such spatial arrangement is called coordination polyhedra .
 Limitations of Werner’s s theory
Even though Werner’s theory was able to explain a number of
properties of coordination compounds , it could not answer
1.Why only certain elements form coordination compounds and
not others?
2.Why the coordination sphere/ entity has a definite geometry?
3.Why these compounds possess definite magnetic & optical
properties.
 Valence bond theory
• 1.As per the theory the metal ligand bond arises by the donation of pair of
electrons by ligands to the metal atom/ion.
• 2.In order to accommodate these electrons the metal ion must possess
requisite number of vacant orbitals of equal energy .These orbitals are
obtained by hybridization of the orbitals of the metal atom to give a set of
hybrid orbitals of equal energy.
• 3.The central metal atom then makes available the number of empty orbital
equal to its coordination number for the formation of co-ordinate bonds with
suitable ligand orbitals.
• 4.Metal - ligand bonds are then formed by the overlap of these orbitals with
those of the ligands I.e . donation of electron pairs by the ligands to the empty
hybridized orbitals . Consequently these bonds are of equal strength and
directional in nature..
• 5. Octahedral, square planar and tetrahedral complexes are formed as a
result of d2sp3 OR sp3d2, dsp2 & sp3 hybridization respectively of the
central metal atom / ion.
 IUPAC names
• 1.Na[PtIBr(NO2)(NH3)] -sodiumamminebromo-iodonitrito-N-
platinate(IV).
• 2.Zn[Co(SCN)4] -zinctetrathiocyanato-S-cobaltate(III)
• 3.[Co(en)3]I3 -tris(ethane1,2diammine)cobalt(III)iodide.
• 4.[Pt(NH3)4][PtCl4] -tetraammineplatinum(II)tetrachloroplatinate(II)
• 5.[CrCl2(H2O)4]NO3 – tetraaquadichlorochromium(III)nitrate.
• 6.Fe4 [Fe(CN)6]3- - ironhexacynaoferrate(III)
• 7.[Co(CN)6]3- -hexacyanocobaltate(III)ion.
• 8.K[PtCl3(NH3)] - potassiumamminetrichloroplatinate(II)
 Octahedral complexes(coordination number =6)
• 1.Formation Of [Cr(NH3)6]3+

• The oxidation state of chromium in [Cr( NH3) 6]s +3. The electronic
configuration of Cr is [Ar] 3d5 4s1.Hence , we have

Cr3+ ion provides 6 empty orbitals to accommodate six pairs

• of electrons from 6 molecules of ammonia .The resulting Complex
[Cr(NH3)6]3+ involves to d2Sp3 hybridization and it is thus octahedral.
• The presence of these unpaired electrons in the complex explains
paramagnetic character.
• 2.Formation of ferricyanide ion , [Fe(CN)6]3-.

• Oxidation state of Fe in this complex ion is +3.Hence we

• Have
•
• The resulting complex involves d2sp3 hybridisation and is
thus octahedral complex .Due to the presence of one unpaired
electron ,it should be slightly paramagnetic in nature.

• 3.Formation of ferrocyànide ion. Fe (CN)6 4-

• Oxidation state of Fe here is 2+.Hence , we have
• 3.Formation of ferrocyànide ion. Fe (CN)6 4-
Oxidation state of Fe here is 2+.Hence , we have
• The resulting Complex ion (involving d2Sp3 hybridization) is
octahedral &diamagnetic as it does not contain any unpaired
electron.
4.Formation of [CoF6]3-
Oxidation state of cobalt in this complex is+3 .Hence we have
KEY POINTS
1. It provides a weak ligand field and it is unable to pair up the
unpaired electrons of the 3d orbitals. Hence. six equivalent
hybrid orbitals are obtained by mixing up of one 4s ,three 4p , &
two 4d orbitals .The highly paramagnetic in nature of the
complex ,confirms the presence of four unpaired electrons.
2. As d- orbitals of the outermost shell take part in hybridisation,
the complexes thus formed are called outer orbital complexes.
3. Note: In the case of the complex [Fe(H2O)6]2+, as H2O is a
weak ligand, electrons in 3d subshell of Fe (II) or Fe(III)will not
pair up. Hence the hybridisation in this case also sp3d2& these
will also be outer complexes.
 Inner and Outer orbital complexes
• Inner orbital complex
• When the complex formed involves the inner (n-1)d orbitals for
hybridization (d2 Sp3 ) the complex is called inner orbital Complex or
hyperligated complex In this case the electrons of the metal are made to
pair up ,so the complex will be either diamagnetic or will have lesser
number of unpaired electrons .This type of complex is also known as low
spin complex.
• Ex: [Co(CN)6]4-
 Outer orbital complex.

• When the complex formed involves the use of outer nd – orbitals for
hybridization (sp3d2) the complex is called outer orbital complex or
hypoligated complex .
• The complex will have larger number of unpaired electrons as the
configuration of the metal remains unchanged This type of complex is
also called high spin complex
• Ex:[ CoF6]3- , [Ni(H2O)6]2+
 Tetrahedral complexes
• .Formation of [Ni(CO)4]0.
• Oxidation state of nickel in this complex is 0.Its electronic configuration
is [Ar] 3d8 4s2.Hence we have
[Ni(CO)4]-Tetrahedral complex
 Square planar complexes
• Formation of [Ni(CN)4]2-
• The oxidation of Ni is +2 .
[Ni(CN)4]2-
 Limitations of valence bond theory
• 1. It cannot explain the colour and spectra of complexes .
• 2.The theory gives a rough idea about the magnetic behaviour of a
complex from the knowledge of the number of unpaired electrons but does
not explain the variation of magnetic moment with temperature.
• 4. It does not give an idea about the Kinetic stability of a complex.
• 5. As per this theory, we cannot distinguish between a strong field ligand
and weak field ligand.
 Crystal Field Theory
• This theory was developed by Hans Bethe and John Van Vleck .

Key points
• 1. Where as valence bond theory considers the metal -ligand bond to be
covalent, crystal field theory considers the bond to be ionic arising purely
from electrostatic interactions between the metal ion and the ligands.
• 2.As interactions are similar to those between the ions in a Crystal, that is
why it has been named as crystal field theory.
• 3.If the ligand is an anion ,then as the metal ion is a cation the forces of
attraction are due to opposite charges . If ligand is a neutral molecule like
NH3, H2O etc. the negative ends of their dipoles are attracted towards the
central metal cation.
• 4. According to this theory, in a free transition metal ion all the
five d orbitals have equal energies (they are degenerate) .This
degeneracy is maintained if the negative charges present
around the central metal atom /ion form a spherically
symmetrical field .
• However if the negative field is due to ligands which may be
anions and or polar molecules such as H2O ,NH3,etc with their
negative ends towards central metal atom/ion the field no
longer remains symmetrical .
• Consequently the degeneracy is split. The pattern of splitting
depends upon the nature of the crystal field exerting its
influence on the central metal atom/ion.
 Crystal field theory for octahedral complexes
• Representing the ligands by small negative
charges and the metal ion has a positive charge,
the geometry of octahedral complex may be
represented
• Compare the shapes of d- orbitals with octahedral
arrangement of ligands ,we can see the lobes of orbitals
• dx2-y2 & dz2 point along x ,y ,z axis while those of
orbitals ,dxy, dxz, dyz point between the axes.
• This shows that the five d- orbitals forms two sets each
containing 2 and 3 orbitals respectively.
Shapes of d-orbitals
• As the ligands approach the metal atom there is repulsion
between the ligands and the orbitals thereby raising their
energy relative to that of the free ion.

• The mean value of the energy of these perturbed d – orbitals is

taken as zero. This is sometimes called as the Bari centre.
• However as. dx2-y2. & d z2 orbitals have lobes along the axis ,
hence they point towards the ligands whereas the lobes dxy,
dxz, dyz orbitals lie between the axes , hence lie between
the ligands .As a result the repulsions between the ligands
and the dx2-y2 & dz2 orbitals are greater than repulsion
between the ligands and the remaining three d – orbitals.
• Consequently the energies of dxy, dyz, dxz orbitals are lower
than those of dx2-y2. & dz2 orbitals. The former 3 orbitals of
lower energy are called t2g orbitals which are three - fold
degenerate and and latter 2 of higher energy are called
• eg orbitals which are two-fold degenerate.

• The difference of energy between the two sets of d orbitals is

called crystal field splitting energy or Crystal Field
Stabilization energy (CFSE) It is usually represented by o It
is found that eg orbitals are +0.6 o or3 /5 o above the
average energy level and t2g orbitals are -0.4 o or -2/5 o
below the average energy level .
1. For any given metal cation the magnitude of o depends upon the
nature of the ligand .Some ligands produce strong fields and hence the
splitting is large where is some others produce weak fields and hence
they result in small splitting of d - orbitals. The experimentally observed
values of some of the ligands in increasing order are given below
2. I-< Br- <S2-< SCN- <Cl-< F- <OH- < C2O42- <O2- <H2O<NCS- <NH3<en<
NO2- <CN-<CO.
3. This arrangement of ligands in order of their CFSE values is known as
spectroelectrochemical series.
• When a metal has only one electron (d1)
• for Ex: [Ti(H2O)6]3+, then the electron is present in one of
the lower t2g orbitals.
• In d2 and d2 entities the three t2g orbitals are filled singly in
accordance with Hunds rule .
• For a d4 ion there are two possibilities - the fourth electron
may enter an eg orbital of higher energy ( t32g e1g ) or may
pair an electron in a t2g orbital ( t42g) .
• The exact configuration adopted is governed by the relative
magnitudes of o and P .(P is the energy needed to cause
pairing of an electron in an orbital)
• If o < P then the fourth electron goes to eg orbital as energy
needed for pairing is more .This is called a weak field , high
spin situation .
• If. o > P then pairing occurs in t2g orbitals. This is called a
strong field, low spin situation.
Octahedral complexes
 Tetrahedral complexes
• In tetrahedral complexes the direction of approach of ligands
is different, the t2g orbitals are closer to the ligands than the
eg orbitals .Thus the crystal field splitting in tetrahedral
complexes is the opposite to that in octahedral complexes.
Tetrahedral complexes
 Magnetic properties of coordination
compounds
• Coordination compounds may be paramagnetic or diamagnetic in
nature para magnetism arises due to the presence of unpaired
electrons if no unpaired electrons are present the compound is
diamagnetic.
• For Ex: In Ti3+ (d1) V3+(d2) & Cr3+(d3), the magnetic moment of
the coordination compound is equal to that of the corresponding
free ion .For this metal ions ,two vacant 3d -orbitals are available
to hybridize with one 4 s and three 4 p orbitals to give 6 hybrid
orbitals needed for octahedral geometry.
• When the metal ion has more than 3 d electrons, the required number of
d orbitals needed for octahedral hybridization (d2sp3) is not available.
A vacant pair of d orbitals in such cases may result by the
redistribution of electrons in d orbitals .Thus in d4 system
(Cr2+, Mn3+) one of the d electrons pairs up leaving two unpaired
electrons while in d5 system ( Mn2+, Fe3+)& d6 system (Fe2+,
Co3+) two &three electrons pairs up leaving one & zero unpaired
electrons respectively. Hence in such cases the magnetic moment
the coordination compound does not tally with that of the free metal ion.
• All coordination compounds involving d4 ,d5 and d 6 metal ions do
not show similar magnetic properties.
• For example :
• Magnetic studies reveal that [Fe(H2O)6]3+ has 5 unpaired electrons
while [Fe(CN)6] 4 – has one unpaired electron.
• [Co(NH3)6]3+ is diamagnetic while [CoF6]3- has four unpaired
electrons. Thus the the magnetic behaviour changes with the nature
of ligand .
• The ligands which induce pairing of the 3d electrons form inner orbital
complexes exhibiting d2sp3 hybridization ,in case of ligands which
do not cause pairing of the 3d eIectrons , complexes are of the outer
orbital type sp3d 2 where the metal utilizes 4d orbitals
• The magnetic moment of an ion in a complex is given by
μ = n(n+2), where n is the number of unpaired electrons.
[BM stands for Bohr’s Magneton].
• Q1 : Find the expected magnetic moment for tetrahedral and
Square planar complexes of Ni (II)and Co (II)?
• Ni(II) has d8 configuration & in tetrahedral complexes will
have 2 unpaired electrons.
• Therefore its magnetic moment will be μ n ( n+2 )
• =2x4 = 2.8 BM.
• Ni (II)in square planar compexes, has no unpaired electron& is
diamagnetic.
• Co(II) has d7 configuration and in tetra hedral complexes will
have unpaired electrons j.e n= 3
• μ 3(3+2)=3.87BM
• Co(II) in square planar complexes will have one unpaired
electron ,i,e. n=1
• μ 1(1+2) =1.73 BM
• Q2:The spin only magnetic moment of [NiCl4]2- is 2.83 BM. Predict
the geometry of the complex?
• The coordination number of Ni (II) in the above complex is 4 & the
geometry can be tetrahedral or square planar .
• The number of electrons in the 3d orbitals of Ni (II) is 8.Square
planar geometry involves dsp2 hybridization. In these the d
electrons will get paired & occupy four orbitals leaving the fifth
vacant to accommodate an electron pair from the ligand & the
complex will be diamagnetic.
 Colour in coordination compounds

• Coordination compounds of transition metals display a range

of colours .
• Absorption of light at a specific wavelength in the visible part
of electromagnetic spectrum causes excitation of a
d- electron from a lower energy orbital to a higher energy level.

When the electrons returns to the original level , the energy

absorbed is emitted. As the energy difference depends on the
nature of the metal, the ligands and oxidation number.
• Ex: The ion [Ti(H2O)]3+ shows an absorption maximum 498 nm & is
violet in colour .This is an octahedral Complex of Ti(III) which has a
single d- electron in a t2g level and the configuration may be
represented as t2g1 eg0 .
• By absorbing energy corresponding to the blue green region of the
spectrum ,the single d- electron is promoted to the eg level and the
configuration of the excited state is t2g 0 eg1.
• This type of electronic transition is called at d-d transition and it
arises due to the splitting of d- orbitals .Crystal field splitting will
not occur in the absence of ligands and thus anhydrous CuSO4 is
colourless .
• The magnitude of crystal field splitting depends on the ligand and
thus the colour of a complex changes with the ligand.
d-d transition
Colour of the coordination complexes
• The CFT was successful in explaining the colour, magnetic
properties, the effects of weak and strong field ligands etc.
• Limitations of Crystal Field theory:
• 1.As ligands are considered as point charges, the anionic ligands
should exert greater splitting effect . However, actually the anionic
ligands are present at the low end of the spectrochemical series.
• 2.It treats the metal –ligand bond as purely ionic bond and does not
take into account the covalent character of the bond.[ These
limitations have been explained by Ligand Field theory and
Molecular orbital theory].
 Stability of coordination compounds
The stability of a complex in a solution refers to the degree of association between the two
species involved in the state of equilibrium.
The magnitude of the( stability or formation) equilibrium constant for the association,
quantitatively expresses the stability. A coordination compound generally does not
dissociate appreciable in a solution the extent of dissociation depends upon the strength
of metal ligand the stability of a coordination compound is measured in terms of its
stability constant.Thus ,if we have a reaction of the type:

M + 4L ML4

• M +L  ML K1= [ML] / [M] [L]

ML+L  ML2 K2= [ML2] / [ML][L]
• ML2+L  ML3 K3= [ML3] / [ML2] [L]
• ML3+L  ML4 K4= [ML4] / [ML3] [L].
• Where K1, K2, K3,K 4 , etc. are referred to as stepwise
stability constants .Alternatively we can write the overall
stability constant
• M+4L ---- ML4
• The stability constant are the equilibrium constant of the
reaction is denoted by
• β = [ML4] / [M] [L]4
• The stepwise and overall stability constant are therefore
related as follows
• β= K1.K2.K3.K4.
• In general
• βn= K1.K2.K3.K4…………Kn.
• The stepwise and overall stability constants are generally
expressed as logK 1 log K2 ……log Kn .The stability of a
coordination compound is directly proportional to its stability
constant.
• There is a decrease in successive stability constants.
• The reciprocal of the stability constant is referred to as a
dissociation constant or instability constant and gives a
measure of the extent of dissociation of the complex.

• Q: The overall stability constant β6 for [Ni(NH3)6]2+ is

• 9.98x 10 7 . Calculate the dissociation constant for the same?
• sol:The overall dissociation constant is the reciprocal of the
overall stability constant I.e 1/ β6 = 1/ 9.98 x 10 7

• = 1.002 x 10 -8.
 Metal carbonyls
• Metal carbonyls are the organometallic compounds in which
carbon monoxide (CO) acts as the ligand.
• Carbonyls maybe homoleptic or heteroleptic.
• In homoleptic carbonyls, the metal is bonded only to carbonyl
ligands whereas in heteroleptic carbonyls the metal is attached
to other ligands , in addition to carbonyl.
• Most of the transition metals form stable homoleptic carbonyls.
• Ex: [Ni (CO)4], [Fe (CO)5] , [Cr(CO)6 ], [Co2(CO)8],
• [Mn 2 (CO)10].
 Bonding in carbonyls
• The bonding in metal carbonyls may be considered to be in two step
process .The metal –both carbon bond in metal carbonyls possess
both σ &  character
• In the first step , a weak σ bond is formed by the donation of electrons from the
carbonyl ligand to a vacant hybrid of the metal.
• In this process carbon monoxide acts as a weak electron pair donor (Lewis base
).The weak σ bond is strengthened by  bonding which is the second step .
• In this step the filled d- orbitals of the transition metal overlap with a vacant
antibonding (π *)molecular orbital of carbon monoxide. (back bonding
occurs).Here CO is also an electron pair acceptor ligand (Lewis acid ).The effect
of σ bond formation strengthens the  bond and vice versa . This is called synergic
effect. Thus, as a result of synergic effect , the bond between CO and metal is strengthened.
• The mononuclear carbonyls( involving one metal atom ) have
simple structures like octahedral,trigonal bipyramidal,
tetrahedral etc.
• In Mn2 (CO)10 , pyramidal MN (CO)5 units are joined by an
Mn –Mn bond.
• In Co2 ( CO)8 ,there is a Co-Co bond & two carbonyl s groups
act as a bridge between the metal atoms .
Structure of carbonyls
THANK YOU

Mrs. LIJI ELIZABETH.