Co-Ordination Compounds

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Simple Salt

Formed by the neutralization of acid and alkali.

(eg)NaCl

Simple salts ionize when dissolved in water.

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Molecular or Addition compounds

• Two or more simple salt solutions are mixed in

stoichiometric proportions
• Allowed to evaporate ,
• Crystals of new compounds formed-Molecular or
Addition compound

 Double salts
 Coordination Complex

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Double Salts

• Exist only in crystal lattices

• When dissolved forms constituent compounds

(eg) Carnallite :KCl.MgCl2.6H2O

Mohr’s salt : FeSO4.(NH4)2SO4. 6H2O
Potash alum :K2SO4Al2(SO4)3.24H2O

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Coordination Complex

• retain their identities when dissolved

• properties are completely different

from those of the constituents

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Complexes

•A central metal atom

bonded to a group of
molecules or ions is a
metal complex.
•If the complex bears a
charge, it is a complex
ion.
•Compounds
containing complexes
are coordination
compounds
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 Complexes

Central Ion
• Central ion acts as an acceptor (Lewis acid)
• must have empty orbitals
Ligand
• Any atom /ion / molecule which is capable of donating
a pair of electrons(Lewis base) to the central atom
• the particular atom which actually donates the electron
pair is called the donor atom
• The ligand containing one donar atom-Uni/Monodentate
two –bidentate
more donor atoms – multi/Poly dentate respectively.

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Uni / Mono dentate

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Bidentate (chelates)
Ligands
 a ligand bonded to a central metal atom at two or more points.

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Polydentate Ligands

Ethylenediaminetetraacetate ion (EDTA)-6 donar

atoms

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Polydentate Ligands

 Chelating agents generally form more stable complexes than

do monodentate ligands
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Chelating Agents

• render metal ions

inactive without
actually removing
them from
solution.
 Phosphates are
used to tie up Ca2+
and Mg2+ in hard
water to prevent
them from
interfering

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Chelating Agents

• Porphines are tetradentate

ligands
(eg) Heme, Cytochrome Oxidase
and chlorophyll are porphyrins.

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common polydentate ligands

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COORDINATION NUMBER

• The total number of ligands attached to the central ion

(eg)

[Ag(NH3)2]+ - coordination numbers 2

[Cu(H2O)4]2+ - coordination numbers 4

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COORDINATION SPHERE

• The central metal atom and the ligands

directly attached to it are collectively
termed as the coordination sphere.
• Coordination sphere is written inside
square bracket
(eg) [Co(NH3)6]3+

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OXIDATION NUMBER

• It is a number which represents the electric

charge on the central metal atom of a complex
ion

(eg) Oxidation number of

Fe in [Fe (CN)6]4-- is +2

Co in [Co(NH3)6]3+ is +3

Ni in Ni(CO)4 is zero
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Complex ions: Structural
Types

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Three common structural
types

Octahedral Tetrahedral Square

planar
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Bonding in co-ordination Compounds

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Valence Bond Theory

• Overlap of filled ligand orbitals with vacant

metal orbitals to form coordinate covalent
bond

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 Octahedral Geometry

[CoF6]3– : four unpaired electrons, which makes it

paramagnetic and is called a high-spin complex.
Co : [Ar]3d 74s2
Co3+ : 3d6

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[CoF6]3–

• The d orbitals used are the 4 dx2-y2 and 4dz2

• the outer 4d orbitals are used for bonding this is
called an outer orbital complex.
• The energy of these orbitals is quite high -
reactive or labile.

• The 3d level contains the maximum number

• of unpaired electrons for a d 6 arrangement-
high-spin or a spin-free complex.

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magnetic moment, μ

μ = √n(n+2) BM

For [CoF6]3– μ = √4(4+2) BM=4.9BM

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[Co(CN)6]3–

• Diamagnetic- low spin complex

• Inner orbital complex-low energy-stable

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Octahedral Geometry

[Fe(CN)6 ]3– with one unpaired electron

Fe+3 d5

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Octahedral Geometry

[FeF6]3– with 5 unpaired electrons

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Octahedral Geometry

• Outer orbital complex-high energy-

high spin
• More no of unpaired electrons-
paramagnetic

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Corodination number - 4

Sp3- tetrahedral dsp2-square planar

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[NiCl4 ]2-

Ni - [Ar]3d 84s2
Ni 2+ - [Ar]3d 8

 Two unpaired
electron
 Outer orbital
 High spin

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[Ni(CN)4 ]2-

• Inner orbital complex

• Diamagnetic

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Limitations of VBT

• Fail to explain the colour of the

coordination complexes( electronic
spectra)

• change in the magnetic properties with

temperature was not explained.

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 Crystal Field Theory

• Metal ion(M) & ligands(L) are

considered point charges
• interaction between the M and L are
purely electrostatics (ionic)
ion –ion (M and anionic L)
 ion -dipole interaction(M and
neutral L)
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CFT: Splitting of the 5 -d orbitals

• Consider the response of the energy of the d orbitals to

the approach of 6 negatively charged ligands (a “crystal
field”) along the x, y and z axes of the metal

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Crystal Field Theory

 As ligands approaches central metal, repulsion between

e – s of metal & ligands increases energy of the d
orbitals(symmetric field)

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CFT: Splitting of the 5 -d orbitals

In Octahedral field,

Orbitals “on axis”: “energy increases Orbitals “off axis”: “energy decreases”

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CFT: Splitting of the 5 -d orbitals

Bari centre

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Electron Configuration in d-Orbitals

t2g are stabilized by 2/5 Δ0

eg is destabilized 3/5 Δ0

CFSE(oct) = -0.4n(t2g) Δ0 + 0.6n(eg) Δ0

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Crystal Field Stabilization Energy(CFSE)

Ti3+ complexes,
• d1 system
• Configuration is (t2g)1(eg)0

 CFSE = -(1)(0.4)(ΔO) = -0.4 ΔO.

 The complex is stabilized by 0.4 ΔO

V3+ complexes,
• d2 system
• Configuration is (t2g)2(eg)0
 CFSE = -(2)(0.4)(ΔO) = -0.8 ΔO.
 The complex is stabilized by 0.8 ΔO
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Crystal Field Stabilization Energy(CFSE)

Cr3+ complexes

• d3 system
• Configuration is (t2g)3(eg)0

 CFSE = -(3)(0.4)(ΔO) = -1.2 ΔO.

 The complex is stabilized by 1.2 ΔO

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Crystal Field Stabilization Energy(CFSE)

In d4 systems ,
(eg) Cr2+ complexes
Configuration can be (t2g)3(eg)1 or (t2g)4(eg)0

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Crystal Field Stabilization Energy(CFSE)

• Depending on the nature of

the ligands and the metal

 complex could be high-spin or

low spin .

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Electron Configuration in d 4 system

Hund’s rule

Δ<P
Δ>P Stronger Weaker
Ligand high spin d 4
Ligands
low spin d4

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Electron Configuration in d 5 system

For the d5 system,

For high-spin,
(t2g)3(eg)2
CFSE =, -(3 × 0.4 ) +(2 × 0.6 ) = 0

For low-spin,
(t2g)5(eg)0
CFSE = - 5 × 0.4 = -2 Δ o

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Δ0 determination

UV-visible spectrum of [Ti(H20)6]3+

 reddish violet colour

max absorption at 20300cm-1

1kJ mol -1 = 83.52cm -1

I kJ/mol = 83.7cm-1
Δ0 = 20300/83.52
= 243 kJ/ mol

CFSE = - 0.4 Δ0 = 97.2 kJ/ mol

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Complex Colour

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FACTORS AFFECTING MAGNITUDE
OF CRYSTAL FIELD SPLITTING

• The nature of the ligands.

• The charge on the metal ion.
• Whether the metal is in the first,
second or third row of transition
elements.
• Complex shape Octahedral/Tetrahedral
(Δt =4/9 Δ0)

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The nature of the ligands

• Ligands which cause,

 small degree of crystal field splitting -
weak field ligands.
 large splitting -strong field ligands.

• The common ligands can be arranged in

ascending order of crystal field splitting -
the spectrochemical series

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Spectrochemical Series

an experimentally determined

series.

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Spectrochemical Series

A pattern of increasing sigma donation is

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FACTORS
MAGNITUDEAFFECTING
OF SPLITTING
CRYSTAL FIELD
The charge on the metal ion

• The magnitude of Δ increases as the

charge on the metal ion increases.

 For first row transition metal ions, the

values of Δ for M3+ complexes are roughly
50% larger than the values for M2.+
complexes
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FACTORS AFFECTING MAGNITUDE
OF CRYSTAL FIELD SPLITTING

Position of the Metal

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 ?
• Calculate the CFSE of, K4[Co(CN)6]
 Oxidation State of the metal is +2
 No of d electrons -- d7
 Strength of the ligand—Strong
 According to CFT, electronic configuration will
be (t2g)6(eg)1
 CFSE(oct) = -0.4n(t2g) Δ0 + 0.6n(eg) Δ0
 CFSE = -( 0.4x6 ) +( 0.6 x 1 ) = (-2.4+0.6) Δ0
(ie)Complex is stabilized by =1.8 Δ0
 HIGH /LOW SPIN COMPLEXES

Fe+3 d5

CFSE(oct) = -0.4n(t2g) Δ0 + 0.6n(eg) Δ0

For high-spin, (t2g)5(eg)0 For low-spin, (t2g)3(eg)2

CFSE = -( 0.4x3 ) +( 0.6 x 2 ) = 0 CFSE = - 5 × 0.4 = -2 Δ o

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JAHN-TELLER DISTORTION

 the shapes of transition metal complexes are affected by

whether the d orbitals are symmetrically or asymmetriclly
filled.

 If the d electrons are symmetrically arranged, they will

repel all six ligands equally.

Thus the structure will be a completely regular octahedron.

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Symmetrically Arrangement

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Asymmetrical Arrangement

• Distortion caused by
asymmetric filling of the t2g
orbitals is usually too small to
measure
• eg asymmetrically filled then
degeneracy is destroyed
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Jahn-Teller distortion

Any non-linear
molecular system in a
degenerate electronic
state will be unstable
will undergo distortion
to lower its symmetry
and remove the
degeneracy

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Asymmetrical Arrangement

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CrF2 -the crystal structure of CrF2 is a distorted rutile (Ti02)
structure.
Cr2+ is octahedrally surrounded by six F-, and there are four
shorter Cr-F bonds of length 1.98-2, and two longer bonds of
length
2.43 A.
 The octahedron is said to be tetragonally distorted

MnF3 - rutile
[Cu F6 ]4- ?

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Consider d8 configuration, In weak field,
• orbitals are symmetrically filled
• a regular octahedral complex
(eg) [Ni(H20)6]2+ [Ni(NH3)6] 2+ .

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SQUARE PLANAR ARRANGEMENTS

In strong field,
• eg electrons pair up and occupy the lower energy dz2 orbital
dx2-y2orbital empty

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TetragonaI distortion

four ligands can now approach along the +x, -x,

+y and -y directions without any difficulty, as the
dx 2-y 2 orbital is empty

along the +z and -z directions meet very strong

repulsive forces from the filled dz2orbital

 only four ligands succeed in bonding to the

metal-square planar complex

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SQUARE PLANAR ARRANGEMENTS

All the complexes of Pt(+ II) and Au(+ Ill) are

square planar- including those with weak field
ligands such as halide ions.

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TETRAHEDRAL COMPLEXES

A regular tetrahedron is related to a cube

The angle between an egorbital, the central

metal and the ligand is half the tetrahedral
angle = 109°28' /2 = 54°

The angle between a torbital, the central

metal and the ligand is 35°16'

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TETRAHEDRAL COMPLEXES

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CFSE in Tetrahedral Complexes

• The magnitude of the tetrahedral splitting

energy is only 4/9 of the octahedral splitting
energy,
 As a result of the relatively small size of the
tetrahedral splitting energy, there are no low-
spin tetrahedral (ML4) complexes.
 It is always more energetically favorable to put
an electron into a t2 orbital rather than pair it in
an e orbital.

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CFSE in Tetrahedral Complexes

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Tetrahedral complexes

Are favoured,
• ligands are large and bulky-avoid crowing
• regular shape is important- d0 d 2 d 5 d 7 and d 10
• ligands are weak field, and the loss in CFSE is less
• central metal has a low oxidation state

 Many transition metal chlorides, bromides and

iodides form tetrahedral structures .

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Limitations Of Crystal Field
Theory

• Interaction between metal-ligand is purely electrostatic –

Not Always

• takes only d-orbitals of a central atom into account. The s

and p orbits are not considered for the study.

• the theory has no explanation as to why H2O is a stronger

ligand as compared to OH–.

• The theory rules out the possibility of having pi bonding.

• The theory gives no significance to the orbits of the ligands.

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Geometric or Stereo
isomerism

Compounds which contain the same number and types

of atoms but which have different spatial arrangements
of the atoms.
Geometric isomers are possible for both square planar
and octahedral complexes, but not tetrahedral.

Square Planar:
Compound type No. of isomers
Ma2b2 2 (cis- and trans-)

Mabcd 3 (use cis- and trans-relations)

here a, b, c, and d refer to monodentate ligands.

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Geometric or Stereo isomerism

Ma2b2 2 isomers (cis- and trans-)

Finite dipole moment No dipole moment

Cisplatin- anti-cancer agent

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Mabcd Type
cis- and trans- refer to the position of 2 groups relative to
each other.
In the cis- isomer they are "next to each other" i.e. at 90
degrees in relation to the central metal ion,
trans- isomer they are "opposite each other", i.e. at 180
degrees relative to the central metal ion.

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Octahedral

Compound type No. of isomers

Ma4b2 2 (cis- and trans-)
Ma3b3 2 (fac- and mer-)
MAA2b2 3 (2*cis- and 1 trans-)
here a, and b, represent monodentate ligands and
AA is a bidentate ligand.

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Geometric or Stereo isomerism

Ma4b2 2 (cis- and trans-)

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MAA2b2 3 (2*cis- and 1 trans-)

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Optical isomerism

Optical isomers are related as non-

superimposable mirror images and
differ in the direction with which they
rotate plane-polarised light.

Optical isomers are possible for both tetrahedral

and octahedral complexes, but not square
planar.

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Optical isomerism

Optical isomerism is common in octahedral complexes

involving bidentate groups
(eg) [Co(en)2Cl2 ]+

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Optical isomerism

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