BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 25
08 Mar 2019
AY 2018-19, Sem-II
Energetics of Complexation Reactions
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Discussed topics in L-24

Electronic spectroscopy: Orgel diagrams of d4/d6,

d2/d8 and d3/d7 systems
Emission spectra of metal complexes
Sample problems

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Splitting of terms – d1 & d9
Thus we can represent both these cases in a single diagram – Orgel
Diagram

2E or 2E
g
2T or 2T2
2g ONE feasible
transition possible
between any two
2D
levels
2T or 2T2
2g
2E or 2E
g

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Splitting of terms – d6 & d4
d6 = d5+1 = same as d1 system
d4 = d5-1 = inverted d1 system = same as d9 system

5E or 5E
g
5T
2g or 5T2 ONE feasible
transition possible
between any two
5D
levels

5T or 5T2
2g
5E or 5E
g

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 Splitting of terms –d1, d9, d6 & d4
Thus we can represent all of these systems in one single Orgel diagram

ONE feasible
transition
possible between
any two levels for
all of these
systems

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Spectra of d2 systems
For d2 system, the maximum multiplicity arising out the 2 electrons
is TRIPLET (S = 1, 2S+1 = 3)
Out of the possible terms the 3F is the ground term and 3P is the
other triplet term

These two terms, 3F and 3P should be considered for

understanding the electronic spectra for the d2 system

For a d8 system, analogical reasoning is considered

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Splitting of terms for d2 system
Free ion Splitting in Oh field
S A1g
P T1g
D Eg+T2g
F A2g+T1g+T2g
In an octahedral field for d2, the 3F
ground term is split into THREE levels
namely, 3T1g(F), 3T2g and 3A2g as shown
3Pterm is NOT split any further but will
be expressed as a 3T1g(P) level

The origin and nomenclature of these

levels is not in the syllabus
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Orgel diagram for d2 system
3A
2g
3T (P)
1g

3P
3T
2g

3F

3T (F)
1g

The possibility of three SPIN-ALLOWED transitions is thus seen

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Orgel diagram for d2 system
3A
2g
3T (P) 3T
1g 1g (P)

3P

3T 3T
1g (F) 2g

3F
3T
2g

3T (F)
1g

3A
2g

The possibility of THREE SPIN-ALLOWED transitions is thus seen

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Orgel diagram for d8 system
3A
2g
3T (P) 3T
1g 1g (P)

3P

3T 3T
1g (F) 2g

3F
3
3T F
2g

3T (F)
1g

3A
2g

The possibility of THREE SPIN-ALLOWED transitions is thus seen

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Orgel diagram for d8 system
3A
2g
3T (P) 3T
1g 1g (P)

3P

3T 3T
1g (F) 2g

3F
3
3T F
2g

3T (F)
1g

3A
2g

The possibility of THREE SPIN-ALLOWED transitions is thus seen

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Orgel diagram for d2 & d8 system
3A
2g
3T (P) 3T
1g 1g (P)

3P

3T 3T
1g (F) 2g

3F
3T
2g

3T (F)
1g

3A
2g

The possibility of three transitions is thus seen

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 Orgel diagram for d3 & d7 system
d7 = d5+2 = same as d2 system
d3 = d5-2 = inverted d2 system = same as d8 4system
A2g
4T (P)
1g 4T (P)
1g

4P

4T 4T
1g (F) 2g NOTE
For d3 and d7
4T
4F systems, the
2g
ground term is
4F instead of 3F
4T (F)
1g
for d2/d8
4A system
2g

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Orgel diagram for d3/d7 & d2/d8 system

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Electronic spectra - Emission
Decay of the excited state back to the ground state may take place by:
Radiative decay (i.e. the emission of electromagnetic radiation),
Non-radiative decay in which thermal energy is lost,
Non-radiative intersystem crossing to a triplet state
Fluorescence is spin
allowed
Phosphorescence is spin
forbidden

NOTE
The notations S1, S0, T1
are spectroscopic
terminologies, NOT
‘terms’(levels)
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Stability of complexes
In studying the formation of complexes in solution, two kinds of
stability of complexes are generally dealt with
1. Thermodynamic stability: This is a measure of the extent to which
the complex will form or will be transformed into another species
(under certain conditions), when the system has reached
equilibrium. Here, metal-ligand bond energies, stability constant
etc. are very important
2. Kinetic stability: Refers to the speed with which transformations
leading to the attainment of equilibrium will occur. (faster rate of
formation of the particular species)
Kinetic stability discusses rates and the mechanism of chemical
reactions, formation of intermediate complexes, activation
energies for the processes, etc.
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Stability of complexes
Higher the value of equilibrium constant for a reaction, more
stable is the product formed.

TYPES:
1. Stepwise formation constant
2. Overall formation constant

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Stepwise formation constants
M = central metal atom, L = monodentate ligand, n = coordination
number
Stepwise formation constants
M+L ML ; K1 = [ML]/[M][L]
ML + L ML2 ; K2 = [ML2]/[ML][L]
. . .
. . .
MLn-1 + L MLn ; Kn = [MLn]/ [MLn-1][L]

K1, K2, ....... Kn are known as stepwise formation constants

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Overall formation constants

Overall formation constants

M+L ML ; β1 = [ML]/[M][L]
M + 2L ML2 ; β2 = [ML2]/[M][L]2
. . .
. . .
M + nL MLn ; βn = [MLn]/[M][L]n
Each bi represents the overall formation constant of all the
steps till itself (upto ith step). e.g. β2 = K1 . K2
β1, β2,...... βn are known as overall formation constants.

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Relationship between K and β
K’s and β’s are related to one another
β1 = K1
β2 = K1 . K2

β3 = [ML3]/[M][L]3 = [ML]/[M][L] . [ML2]/[ML][L] . [ML3]/[ML2][L]

= K1 . K2 . K3
βn = K1 . K2 . K3 ………. Kn
log βn = log K1 + log K2 + log K3 +……. log Kn
And the overall formation constant is linked with the Gibb’s free
energy change, DG in the formation process
DG = -RTlnb, and DG = DH -TDS

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Inert and labile complexes
In the kinetic sense it is more proper to call the complexes inert or
labile complexes rather than stable or unstable complexes. These
terms were introduced by Taube, based on the difference in rate of
replacement of one ligand by another
• The complexes in which the ligands are rapidly replaced by others
are called labile or non-inert complexes
• Complexes in which substitution occurs slowly are termed inert
complexes
According to Taube’s original definition, if ligand substitution
takes place in < 1 min at 25 °C at 0.1M concentration they can be
called as labile complexes
Kinetic stability terms (labile/ inert) should not be confused with
thermodynamic stability (expressed in terms of b)
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Example: Inert/ labile vs. Stable/
unstable complexes
[Hg(CN)4]2- complex is very stable with b = 1042
But in solution it undergoes rapid ligand exchange with 14CN- ions
with a very fast rate t½ = 30 s
[Hg(CN)4]2- + 4 14CN- [Hg(14CN)4]2- + 4 CN-
Thus stability of a complex is not related to its lability
Another example of kinetically inert and thermodynamically unstable
complex:
[Co(NH3)6]3+ + 6H+ Co3+(aq.) + 6NH4+
The tremendous thermodynamic driving force of six basic ammonia
molecules combining with six protons results in an equilibrium
constants for the reaction of 1025  highly unstable
BUT at room temperature several days are required to undergo this
reaction (degradation of the complex)  highly inert
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Thermodynamic and kinetic stability
[Ni(CN)4]2-, [Mn(CN)6]3-, and [Cr(CN)6]3- : All of these complexes are
extremely stable from a thermodynamic point of view; yet kinetically
they are quite different. Explain the order of the half lives in terms of
the lability or inertness

1. [Ni(CN)4]2- + 414CN- [Ni(14CN)4]2- + 4CN- (t1/2 ~ 30 sec)

2. [Mn(CN)6]3- + 614CN- [Mn(14CN)6]3- + 6CN- (t1/2 ~ 1 h)
3. [Cr(CN)6]3- + 614CN- [Cr(14CN)6]3- + 6CN- (t1/2 ~ 24 days)

Of these complexes, complex 1 exchanges cyanide ligand very

rapidly (is labile), a second is moderately labile, and only [Cr(CN)6]3-
can be considered to be inert

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Factors affecting stability
Both metal centre and the ligand play important role in stabilizing
the complex.
The important factors from the metal’s perspective are,
1. Charge and size of cation: Large charge and small sized metal
ions form more stable complexes – highly charged small
cations allow closed approach of ligands and hence stronger
electroctatic interactions while forming complexes hence
stabler.
E.g. [Fe(CN)6]3- has b= 1031, [Fe(CN)6]4- has b=108

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Factors affecting stability
Both metal centre and the ligand play important role in stabilizing
the complex. The important factors are,
2. Crystal field effect and natural order of stability: Stability of
the high spin complexes of d5 to d10 (1st row) are somewhat
consistent with the order of their charge/radius ratio

Irving-William series:

Order of radii :

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 Factors affecting stability
Irving-William series:
Order of radii :
-C

• The trend peaks at Cu2+ (d9) and not at Ni2+ (d8)

• We expect rion to decrease from Mn2+ to Zn2+ as Zeff increases, but
Ni2+ being smallest. In turn, this predicts the highest value of logbn
for Ni2+
• Why are Cu(II) complexes so much more stable than might be
expected? The answer lies in the Jahn–Teller distortion that a d9
complex suffers creating better stability
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 Factors affecting stability
Irving-William series:
Order of radii :

Stepwise stability
constants (logKn) for
the displacement of
H2O by NH3 from
[Ni(H2O)6]2+ (d8) and
[Cu(H2O)6]2+ (d9)

For the first 4 substitution steps, complex stability is greater for Cu2+
than Ni2+ , reflecting the formation of four short (strong) Cu-N bonds.
The value of logK5 for Cu2+ is consistent with the formation of a weak
(axial) Cu-N bond; logK6 is indeterminate
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Factors affecting stability
The important factors from the Ligand’s perspective are,
1. Charge and size of Ligand: Large charge and small sized
ligandsl (mostly anions) form more stable complexes –
evident from their b values. E.g. [FeF]2+ has b= 106, [FeCl]2+
has b=20.
For neutral (monodentate) ligands, higher the dipole moment
and smaller size, the stabler is the complex
2. Basicity : higher is the basicity better in the ability of
formation of coordination bonds thus stabilizing the complex
better.
3. Chelate effect: Formation of chelate rings imparts better
stability than a non-chelating ligand
4. Size of chelate ring – Macrocyclic effect
5. Steric effect: steric environment around the donor centre
guides the efficiency of binding , hence the stability
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An example

[Cu(NH3)4]2+ < [Cu(en)2]2+ < [Cu(trien)]2+

Log β = 12.7 < 19.7 < 20.5

- RT ln β = ΔG0 = ΔH0 – TΔS0 (ΔH0 is negative)

(i) Cd2+ + 2en [Cd(en)2]2+ with log β = 10.6

{ΔH0 = -56.3, ΔS0 = +14.1, - TΔS0 = -4.2 and ΔG0 = -60.7}

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Discussed topics……

Stability of metal complexes

Thermodynamic and Kinetic Stability
Factors affecting stability
Examples

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Announcement
Meet the ICs
An interactive session organized by ACC, Pilani Campus
ALL First year courses’ ICs will be meeting you
Date: 08 Mar 2019, Friday
Time: 6.30 pm – 7.30 pm
Venue: SR Bhawan Common Room Block A

Dear Students;
You are welcome to make maximum benefit of the session to plan
and organize your Mid-sem examinations

With best wishes,

ACC, team

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