Unit I- Coordination

Chemistry
For BTech.
Coordination Chemistry – Branch of chemistry that deals with the study of
coordination complexes

•Coordination complexes have been known since the beginning of modern chemistry.
•Early well-known coordination complexes include dyes such as Prussian blue.
•Early contributions: Swedish chemist Christian Wilhelm Blomstrand and Danish
chemist Sophus Mads Jørgensen.
•The most widely accepted version of the theory today was published by Alfred
Werner (Nobel prize in Chemistry in 1913)

Difference between a double salt and a co-ordination compound

Simple Salt

Complex compound
 Monodentate ligands can be further classified into three types based on their charge
1)

2)

3)

b)

(1)
(1) (2)

(2)
c
 d) Polydentate Ligands:

When several donor atoms are present in a single ligand, the ligand is said to be
polydentate.

Ethylenediamine tetracetate ion (EDTA) 4-

Denticity = 6 (hexa dentate ligand)

EDTA-Metal complex

(1) (4) EDTA-Metal complex

(5)
(2)

(3) (6)
Point to note: M+ can be Ca2+ (or) Mg2+

We will use this concept in experiment 3 of our practical to determine hardness (Ca 2+) of water
using EDTA – Complexometric method.
 Werner’s Theory
Werner postulated that metal ions have two different kinds of valency:
1. Primary valency = oxidation state of the metal ion
2. Secondary valency = Coordination number

Coordination number = number of bonds formed between the metal ion

and the ligands in the complex ion. It can range from 2 to 9.
• 6 and 4 (most common)
• 2, 5 and 8 (less common)

Ligands
• The molecules or ions coordinating to the metal are
the ligands.
• They are usually anions or polar molecules.
• The must have lone pairs to interact with metal

Coordination number = 6
Please refer to the class notes for the geometry of
coordination complexes (ML2 to ML6) with
coordination numbers from 2 to 6 and their
examples.
 Crystal Field Theory (CFT)
This theory is based on the concept that when the negative charges of the incoming
ligands (or the negative ends of dipolar molecules like NH3 and H2O) attract the
positively charged metal ion, there is also repulsive interaction between the d-electrons
present on the metal ion and the ligands. Certain assumptions are taken while dealing
with CFT.
1. The ligands are treated as point charges.
2. The interactions between metal ion and ligand are treated as purely electrostatic
(ionic) , no covalent interactions are considered. (Covalent nature is considered in
Ligand Field Theory, and Molecular Orbital Theory).
3. In isolated gaseous metal ion, all of the five d-orbitals are degenerate.
4. When a hypothetical spherical field of ligand approaches the metal ion, d-orbitals still
remain degenerate (same energy), but their energy level is raised a bit due to
repulsion between the orbitals of metal and ligand. This energy level is called Bary
center.
5. The most common geometry of transition metal complexes are octahedral,
tetrahedral or square planar etc.. The field provided by the ligands is not at all
spherically symmetrical. Therefore, the d-orbitals are unequally affected by the
ligands, and degeneracy of the d-orbitals in metal is removed and split into different
energy levels (e.g. t2g or eg).
How Orbitals will be affected when ligands approach a metal in
an octahedral arrangement

Ligands with their pair of electrons

approach to the metal along the X, Y and Z
axes for an octahedral complex formation
d-orbitals having lobes pointing directly at x-, y-
and z-axis (yellow colour) are repelled most by
electron-electron repulsion.
Bary center

d-orbitals not pointing directly at x-, y- and z-axis (red

colour) are stabilized to maintain the overall energy
same
 eg
Splitting of d orbitals??

t2g

1. Degenerate means having same energy

t refers to triply degenerate level orbitals

three d-orbitals

the "g" = gerade; german for even ; eg means doubly degenerate

t2g = triply degenerate orbitals. even number of electrons - same symmetry

2. eg = exempli gratia in latin

 Crystal Field Effects on Octahedral
Complexes
Bary center

The energy gap between eg and t2g is called crystal field splitting energy and it is
denoted
Points by Δo or Δoct or 10 Dq, where Δ represent Crystal field splitting energy,
to note:
"o" in Δo is for octahedral.
Because
1. The the overall
difference energy
in energy is maintained,
between the
the eg and theenergy of the(Δthree
t2g orbitals O
t2g orbitals
) is called are
the crystal
lowered
field or stabilised
splitting by 0.4 Δo (4 Dq) and the energy of the two eg orbitals are
energy (CFSE)
raised or repelled by 0.6Δo (6 Dq) with respect to hypothetical the spherical crystal
2. Δ is or
field
O
often
Baryexpressed
Centre. in terms of an energy parameter called 10 Dq.
 Crystal Field Effects on Tetrahedral Complexes
In a tetrahedral crystal field, imagine four ligands lying at
alternating corners of a cube
The dx2-y2 and dz2 orbitals on the metal ion at the center
of the cube lie between the ligands, and the dxy, dxz, and
dyz orbitals point toward the ligands. As a result, the
splitting observed in a tetrahedral crystal field is the
opposite of the splitting in an octahedral complex.

0.4Δ t

Because a tetrahedral complex has fewer ligands, the

0.6Δ t
magnitude of the splitting is smaller. The difference
between the energies of the t2g and eg orbitals in a
tetrahedral complex (Δt) is slightly less than half of the
splitting in analogous octahedral complexes (Δo).
Δ t = 4/ 9 Δ o
 Tetrahedral Crystal Field

the splitting observed in a tetrahedral crystal field is opposite of

splitting in octahedral complex.

0.6
Δo 2 0.4
Δo
3
0.4 0.6
Δo Δo

Δ t = 4/ 9 Δ o
 1
We focus on d to d 10 Ti3+ => d1 system
Transition metals

eg t2g

Energy

1 KJmol-1 = 83.7 cm-1, eg

Δo = 20300/83.7 = 243 KJmol-1

t2g
How to draw the complementary color wheel?

= 12500 cm-1
800 nm 650 nm

R O
= 25000 cm-1 400 nm 600 nm

420 nm V Y
I
B G 560 nm
450 nm

490 nm
Complementary colours will be emitted

x nm = 10,000,000 / x cm–1 For eg. a complex which absorbs light in

y cm–1 = 10,000,000 / y nm the wavelength 400 (V) to 450 nm (I)
would emit yellow (Y)
Problems related to color determination of the complexes

1. Calculate the wavelength of a light having wavenumber 24000 cm-1?

2. Find out the wavelength and color of the compound having a gap between t2g and eg
in 239.23 KJ mol-1 (1 kJmol-1 = 83.6 cm-1)

To work out these problems you need to know the following relationships.

-
 Factors Affecting The Magnitude of ∆

3d
4d The order of Δ along the groups 5d > 4d > 3d
5d

Δo
Δt

(electrostatic field produced by different ligands are different) diff. field strength)

Weak - - Strong
 Spectrochemical Series (strength of ligand interaction)

Increasing Δ

Weak - I- < Br- < SCN- (S-bonded) < Cl- < F- < OH- < C2O42- < O2- < H2O < NCS-
(N-bonded) < py < NH3 < en < 1,10-phenanthroline < NO2- < PPh3 < CN- < CO -
Strong
• Weak field ligands: H2O, F−, Cl−, OH−
• Strong field ligands: CO, CN−, NH3, PPh3

Increasing Δ

3d3 3d3
3d3 3d3
 Crystal Field Stabilization Energy (CFSE)
▪ The energy difference between the distribution of electrons in a particular crystal
field and that for all electrons in the hypothetical spherical or uniform field levels
is called the crystal field stabilization energy (CFSE). [relative to their mean
energy, Bary Centre]
CFSE ∆0 = number of electrons in t2g x -0.4 + number of electrolns in eg x 0.6

For [Ti(H2O)6]3+ ion, the CFSE is 0.4 * 243 KJmol-1 = 97 KJmol-1

Hence, the complex is stable.
Metal ions with d4, d5, d6, or d7 e- configurations can be
either high spin or low spin, depending on magnitude of Δo

Magnitude of Δo
Large Δo = low spin complex
Smaller Δo = high spin complex
CFSE for d4 system:
• For high spin, CFSE = 0.6 Δo
• For low spin, CFSE = 1.6 Δo
As Energy difference increases, electron configuration changes
“Low spin”
“High spin”
Number of unpaired
electron = 4

Number of unpaired
electron = 0

Co(III) is d6
CFSE = Number of electrons in t2g × (−0.4) Δo + Number of electrons in eg ×
(0.6) Δo

Calculate the Crystal Field Stabilization Energy (CFSE) of [CoF6]3−.

a) -0.6 Δo b ) 0.6 Δo c) -0.4 Δo d) 0.4 Δo

Solution : Hybridisation of Co in ground state : 3d7 4s2

Hybridisation of Co3+ in excited state : 3d6 4s0. Since it is high spin complex

Hence, Co3+ : t2g4 e2g

CFSE = Number of electrons in t2g × (−0.4)Δo + Number of electrons in eg ×

(0.6)Δo

⇒CFSE = 4 × (−0.4)Δo + 2 × (0.6)Δo

⇒CFSE = −1.6 Δo + 1.2 Δo = −0.4Δo
High Spin, Low Spin – the Pairing Energy (P)
In order to force an electron to pair with another an energy called Pairing energy (P) has
to be invested.
This is made up of two terms: (1) the Coulombic repulsion arising out of forcing two
electrons to occupying the same orbital; (2) the loss of exchange energy that occurs as
electrons with parallel spins are forced to have anti-parallel spins.
If P > Δo, the configuration t2g3eg1 is preferred. This is known as weak field or high
spin situation.
If P < Δo , the configuration t2g4eg0 is adopted. This leads to strong field or low
spin situation.
The nomenclature high and low spin arises from the magnetic moment
differences between the two configurations. Thus, t2g4eg0, has only two unpaired
electrons and therefore would have a magnetic moment of 2.83 BM. In contrast
the configuration t2g3eg1 would have four unpaired electrons with a magnetic
moment of 4.90 BM
Δo P
[Fe(H2O)6]2+ d6 9350 19150 High Spin P > Δo
[Fe(CN)6]4- d6 32200 19150 Low Spin P < Δo
 Magnetic Properties of Metal Complexes
Magnetism is caused by moving charged electrical particles (Faraday, 1830s). These
particles can be the current of electrons through an electric wire, or the movement of
charged particles (protons and electrons) within an atom. These charged particles move
much like planets in a solar system:
• nucleus spin around its own axis, causing a very
weak magnetic field.
• electrons orbit around the nucleus, causing a weak
magnetic field.
• electrons spin around their own axis, causing a
significant magnetic field.

Spinning electrons generate the bulk of the magnetism in an atom.

Within each orbit, electrons with opposite spins pair together, resulting in no net
magnetic field. Therefore only unpaired electrons lead to magnetic moment

The spin-only formula (μs)

= √4S(S+1) where, S = n/2

 Magnetic properties: Spin only and effective
The spin-only formula (μs) applies reasonably well to metal ions from the first
row of transition metals: (units = μB,, Bohr-magnetons)

Metal iondn configuration μs(calculated) μeff (observed)

Ca2+, Sc3+ d0 0 0
Ti3+ d1 1.73 1.7-1.8
V3+ d2 2.83 2.8-3.1
V2+, Cr3+ d3 3.87 3.7-3.9
Cr2+, Mn3+ d4 4.90 4.8-4.9
Mn2+, Fe3+ d5 5.92 5.7-6.0
Fe2+, Co3+ d6 4.90 5.0-5.6
Co2+ d7 3.87 4.3-5.2
Ni2+ d8 2.83 2.9-3.9
Cu2+ d9 1.73 1.9-2.1
Zn2+, Ga3+ d10 0 0
 Isomerism in Coordination Compounds
Isomers have the same molecular formula, but their atoms are arranged either
in a different order (structural isomers), or spatial arrangement
• (stereoisomers).
Some Classes of Isomers

Isomers
(same chemical composition, but
different bonding and properties)

Structural Isomers Stereo-Isomers

(different bonds) (same bonds, different
spatial arrangements)

Ionisation Hydrate Coordination Linkage

isomerism isomerism isomerism isomerism Geometric Optical
isomerism isomerism
(cis-trans)
 Structural Isomerism
1. Ionization isomerism
2. Hydrate isomerism
3. Coordination isomerism
4. Linkage isomerism

Ionization isomerism:
• Same overall Composition. But the composition of the coordination sphere
varies.
• Some isomers differ in what ligands are bonded to the metal and what is
outside the coordination sphere; these are also called coordination-sphere
isomers.

• [Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4

• Here, the counter ions (anion) are different. In the former, sulfate
coordinates to metal and bromide is counter ion. In the latter one, opposite
happens.
• Upon ionization, or upon dissolution in water, we get bromide anion in the
former case, where as, we will get sulphate anion in the latter case.
Hydrate (or solvate) isomerism

• Three isomers of CrCl3(H2O)6 are

• The violet [Cr(H2O)6]Cl3,
• The green [Cr(H2O)5Cl]Cl2 · H2O, and
• This is also green [Cr(H2O)4Cl2]Cl · 2H2O. When both the positive and
negative ions are complex ions,
isomerism may be caused by
Coordination isomerism the interchange of ligands
between the anion and cation
• They differ in coordination entities
• For example, [Co(NH3)6][Cr(CN)6] and [Co(CN)6][Cr(NH3)6] are coordination
isomers.

[Co(NH3)6]3+ & [Cr(CN)6]3- [Cr(NH3)6]3+ & [Co(CN)6]3-

• They have same total compositions, but they have different complex entities
(complex ions).

• Another example: [Zn(NH3)4][CuCl4] and [Cu(NH3)4][ZnCl4] compounds are also

coordination isomers.
 Linkage Isomerism
• Composition of the complex ion is the same, but the point of attachment of
at least one of the ligands differs.
• The donor atom of ligand varies

Linkage Isomerism of NO2–

Same ligand, but the donor Nitro- Nitrito-

atom is different

Linkage Isomerism of thiocyanate (SCN−) & isothiocyanate (NCS−)

• linkage isomers are violet-coloured

[(NH3)5Co(SCN)]2+ and
orange-coloured [(NH3)5Co(NCS)]2+

Violet Orange
 Stereoisomer
❖ Geometrical Isomers
• Geometrical isomers are most important for square planar & octahedral
complexes.

Isomerism in Octahedral Complexes

• Only one structure possible for octahedral complexes (if only one ligand is
different from other five): (MA5B)
• since all six vertices of an octahedron are equivalent.
If two ligands in an octahedral complex are different from other four (MA4B2),
two isomers are possible: trans- and cis- isomers.
 Example: Isomerism of octahedral complex [Co(NH3)4Cl2]Cl

Cis-form Trans-form

• Same chemical composition

• Same number of groups of same types are attached to same metal.
 Stereoisomerism
❖ Optical Isomerism: Isomers have opposite effects on plane-polarized light.

❖ Optical Activity
• Exhibited by molecules that have nonsuperimposable mirror images (chiral
molecules).
• Enantiomers – isomers of nonsuperimposable mirror images.

A Human Hand Exhibits a Nonsuperimposable Mirror Image

• Just as a right hand will not fit into a left glove, two enantiomers cannot be superimposed
on each other.
Q: Does [Co(en)2Cl2]Cl exhibit geometrical isomerism?
Yes, => trans- and cis- isomers. en = ethylenediamine
Does it exhibit optical isomerism?
Trans form – No
Cis form – Yes

These two forms are identical (superimposable)

– So, only one trans-isomer possible.
• Optically inactive

Two enantiomers of the cis-form

• Optically active

Two enantiomers of cis-form – these two forms are non-superimposable

 Advantages and Disadvantages of Crystal Field
Theory
Advantages over Valence Bond theory
1. Explains colors of complexes
2. Explains magnetic properties of complexes (without knowing
hybridization) and temperature dependence of magnetic moments.
3. Classifies ligands as weak and strong
4. Explains anomalies in physical properties of metal complexes
5. Explains distortion in shape observed for some metal complexes

Disadvantages or drawbacks
1. Evidences for the presence of covalent bonding (orbital overlap) in metal
complexes have been disregarded.
e.g. it does not explain why CO although neutral is a very strong ligand

2. Cannot predict shape of complexes (since not based on hybridization)

3. Charge Transfer spectra not explained by CFT alone
 Problem solving !!
Cobalt form three octahedral complexes, [CoCl6]4-, [Co(R2NCS2)3] and
[Co(CN)5(H2O)]3-. These have magnetic moments 0, 1.73 and 3.9 BM (not in
the order). Assign the moments to the complexes and predict the relative
strength of the dithiocarbamate ligand.

Solution
• [CoCl6]4- : Co2+, 3d7 ,Cl- weak field ligand, high spin, 3 unpaired e’s , => 3.9
BM
• [Co(CN)5(H2O)]3- : Co2+, 3d7, CN- strong field ligand, low spin, 1 unpaired e,
=> 1.73 BM
• [Co(R2NCS2)3] : Co3+, 3d6 , ligand is strong field, and also higher oxidation
number of the metal, low spin complex, all e’s paired up! => 0 BM.
 Q: Chloro compound of vanadium has only spin magnetic
moment of 1.73 BM. This vanadium chloride has the formula:
a) VCl2 b) VCl3 c) VCl4 d) VCl5

Answer:
Magnetic moment, Where, n = number of unpaired electron.

Μ = 1.73 BM, this gives n = 1

Electronic configuration of V is [Ar]4s23d3. For only one unpaired electron, it has to

be V4+
Hence, the formula of vanadium chloride
is VCl4.
Q. Co[(NH3)6]3+ ion is:
(a) Paramagentic
(b) Diamagnetic
(c) Ferromagnetic
(d) Ferri magnetic.

Q. In K4[Fe(CN)6] the number of unpaired electrons in iron are:

(a) 0
(b) 2
(c) 3
(d) 5.

Q. A complex compound in which the oxidation number of a metal is zero, is

(a) K4[Fe(CN)6]
(b) K3[Fe(CN)6]
(c) [Ni(CO)4]
(d) [Pt(NH3)4]Cl2
Q. The magnetic moment (spin only) of [NiCl4]2- is
(a) 1.82 BM
(b) 5.46 BM
(c) 2.82 BM
(d) 1.41 BM
Q. Among the ligands NH3, en, CN – and CO the correct order of their increasing field
strength, is
(a) CO < NH3 < en < CN–
(b) NH3 < en < CN– < CO
(c) CN– < NH3 < CO < en
(d) en < CN– < NH3 < CO
Q. The spin only magnetic moment value (in Bohr magneton units) of Cr(CO)6 is
(a) 0
(b) 2.84
(c) 4.90
(d) 5.92

Q. The spin only formula (μs) for octahedral complexes is

(a) (4S(S+1))1/2
S = spin angular momentum = n/2
(b) (4S(S+1))1/2 + (L (L+1))1/2
(n = number of unpaired electrons)
(c) (L (L+1))1/2
(d) L(L+1)
Q. Which of the following species will be diamagnetic?
(a) [Fe(CN)6]4-
(b) [FeF6]3+
(c) [Co(C2O4)3]4-
(d) [CoF6]3-
Q. Which of the following octahedral complexes of Co (at. no. 27) will have highest
magnitude of Δoct?
(a) [Co(CN)6]3-
(b) [Co(C2O4)3]3-
(c) [Co(H2O)6]3+
(d) [Co(NH3)6]3+
Q. The magnetic moment of [Co(NH3)6]Cl3 is
(a) 1.73
(b) 2.83
(c) 6.6
(d) Zero
Q. In the complex compound K4[Ni(CN)4] oxidation state of nickel is ?
(a) -1
(b) 0
(c) +1
(d) +2
Q. The spin only magnetic moment value (in Bohr magneton units) of Cr(CO)6 is
a) 0
b) 2.84
c) 4.90
d) 5.92

Q. Calculate the CFSE values for d3 and d8 configurations of weak field octahedral
complexes.
a) 0 Δo and -1.2 Δo
b) 1.2 Δo and -1.2 Δo
c) -1.2 Δo and -1.2 Δo
d) -1.2 and 0
Q. Calculate the CFSE values for d4 and d7 configurations of high spin tetrahedral
complexes.
a) 0 Δo and 0 Δo
b) 0.18 Δo and 0.54 Δo
c) -0.54 Δo and -0.18 Δo
d) -0.18 Δo and -0.54 Δo

Ans: to solve this, you first need to calculate in terms of tetrahedral geometry, and then convert
to octahedral values by: Δt = 4/9 Δo

d4: e2, (t2)2

2 CFSE = (-0.6 x 2) + (0.4 x 2) Δt
= - 0.4 Δt
3 = - 0.177 Δo

d7: e4, (t2)3

CFSE = (-0.6 x 4) + (0.4 x 3) Δt
= - 1.2 Δt
= - 0.533 Δo