BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 19
07 December 2022
AY 2022-23, Sem-I
Introduction to Coordination Chemistry
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Lecture 18 - Summary

LUMO

Benzene π to π*
HOMO

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Lecture 18 - Summary
Because nuclei are so much more massive than electrons, an electronic
transition takes place faster than the nuclei can respond.

Implications
• During an electronic transition, electron density changes rapidly while the
nuclear positions remain the same.
• Because of electron density changes, the original nuclear positions are not
equilibrium positions in the excited electronic state and the nuclear
movement brings in vibrations.

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Lecture 18 - Summary
What happens after absorption??
Non-Radiative Decay:
•Disordered thermal motion of surroundings of the molecule
• Internal Conversion.
 Radiative Decay:
• Direct deactivation
• Fluorescence
• Phosphorescence

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Lecture 18 - Summary

Various intensity of
electronic
transitions

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Lecture 18 - Summary

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Lecture 18 - Summary
Absorbance: Provides
information about the
ground state of the
molecule.

Fluorescence: Provides
information about the
excited state of the
molecule.

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Lecture 18 - Summary

Phosphorescence:
• Intensity is very weak
• Time lag

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Lecture 18 - Summary
Professor Ahmed Zewail
received Nobel Prize in
Chemistry for “his studies of
transition states of chemical
reactions using femtosecond
spectroscopy” (1999). Egyptian-
American chemist, known as the
"father of femtochemistry".

The Nobel prize in chemistry 2014 was

awarded “for the development of super-
resolved fluorescence microscopy” to Prof.
Eric Betzig, Prof. Stefan W. Hell, and Prof.
William E. Moerner.

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Inorganic Chemistry

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 You learned so far (10+2)
• Redox reactions
• Hydrogen and related
compounds
• s-block elements
• p block elements
• d and f block elements
• Metals, non-metals,
Alloy etc.

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Topics to be discussed
7 (14-17) Spectroscopy: (Rotational, Vibrational, Raman and
Electronic): Absorption and Emission, different
regions of electromagnetic spectrum, molecular
rotation, molecular vibrations, normal modes, and
rotational transitions accompany vibrational
transitions, Boltzmann population distribution.
Electronic spectroscopy, Lambert Beer's law
8 (18-20) Coordination Chemistry: Coordination
compounds: Effective atomic no. concept;
Chelates and isomerism; shapes of d-orbitals,
crystal field theory, octahedral complexes,
spectrochemical series, CFSE, Effects of crystal
field splitting
9 (21-23) Distortion of Complexes, Tetrahedral, Octahedral,
and Square planar Arrangements : Jahn-Teller
distortion: Effect of geometrical distortions on
stability, stability in other geometries
10 (24-26) Coordination Chemistry, Electronic spectroscopy
and stability aspects: Electronic spectra of
octahedral complexes, Applications of term
symbols, Thermodynamic and kinetic aspects of
Inorganic complexes during reactions.
T1: 19.1-19.6, 19.7-19.13  Use the concepts of quantum mechanics to
understand the molecular spectroscopy.
20.1-20.8
 Concept of bond stretching, vibration of
molecule.
 Identify spectroscopy as an important tool in
modern science.
R1: p194-200 (SS); p202-214; p222-224, p232-
235
 The concept of chelates and coordination
compounds
 Understanding structure and properties of
coordination complexes in light of various
theories
R1: p214-222  Nature of ligand, idea of different orbitals
and their effect in inorganic complexes
 Idea of distortion in tetrahedral, octahedral,
and square planar complexes
R1: p219-222  Spectral nature of inorganic complexes
 Effect of strength and the symmetry of
R1: p947-960
ligand field on various energy levels
R3: p262-264, 380-381, 385-389  Identify the nature of stable and unstable
complexes
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Pioneer Scientist
 Alfred Werner was a Swiss chemist and a
professor at the University of Zurich.
 He won the Nobel Prize in Chemistry in 1913 for
proposing the octahedral configuration of transition
metal complexes.
 Werner developed the basis for modern
coordination chemistry.
Alfred Werner
 He was the first inorganic chemist to win the
Nobel prize, and the only one prior to 1973
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Coordination Chemistry
• Transition metals act as Lewis acids
• Form complexes/complex ions
Fe3+(aq) + 6CN-(aq)  [Fe(CN)6]3-(aq)
Lewis acid Lewis base Complex ion

Ni2+(aq) + 6NH3(aq)  [Ni(NH3)6]2+(aq)

Lewis acid Lewis base Complex ion

 Complex with a net charge = complex ion

 Complexes have distinct properties
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Addition Compounds
When stoichiometric amounts of two or more stable compounds join
together two types of addition compounds are formed.
(i) Double salts
K2SO4+ Al2(SO4)3+24 H2O  K2SO4.Al2(SO4)3.24 H2O
Double salts lose their identity in solution

(ii) Co-ordination compounds

Fe(CN)2 + 4KCN  Fe(CN)2. 4KCN = K4[Fe(CN)6]
[Fe(CN)6]4- is stable in solution
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Coordination Compounds
Compound that contains Coordination sphere: Metal
one or more complexes and ligands bound to it

[Co(NH3)6]Cl3 or K4[Fe(CN)6]

Coordination number: number of Complex charge = sum of

donor atoms bonded to the central charges on the metal and
metal atom or ion in the complex the ligands
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Werner’s work
 Metal ions exhibit two kinds of valence: primary and secondary

[Co(NH3)6]Cl3 or K4[Fe(CN)6]
 The primary valence is the number of charges on the complex ion,
Non-directional
 The secondary valence is the number of atoms that are directly
bonded (coordinated) to the metal, Directional
 The secondary valence is also termed the “coordination number” of
the metal in a coordination complex
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Classification of Ligands
Ligands: classified according to the number of donor atoms

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An Illustration of Primary and Secondary valency

Conductivity and Cryoscopic Measurement

Formula Cryoscopic Molar Structure

Measurement Conductivity
CoCl3.6NH3 4 particles 6 charges [Co(NH3)6]3+3Cl-
CoCl3.5NH3 3 particles 4 charges [Co(NH3)5Cl]2+2Cl-
CoCl3.4NH3 2 particles 2 charges [Co(NH3)4Cl2]+Cl-
CoCl3.3NH3 1 particle 0 charge [Co(NH3)3Cl3]
Co(NO2)3.3KNO2 4 particles 6 charges 3K+[Co(NO2)6]3-

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Effective Atomic Number (EAN)
Effective atomic number (EAN) rule : based on the octet theory of
Lewis this is the first attempt to account for the bonding in complexes
Sum of the electrons on the central atom (Lewis acid) including those
donated from the ligands (Lewis base) should be equal to the number
of elctrons on a noble gas
[Cu(CN)4]3-
At. No of Cu = 29, Cu = +1, 4 L = 8 electrons gained
EAN = 29-1+8 = 36 (Atomic No. of Kr)  Gives stable compound
 Violated in many places
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EAN: few more examples
Atom At. No. Complex Elec. Lost Elec. Gained EAN
Cr 24 [Cr(CO)6] 0 12 36 (Kr)
Fe 26 [Fe(CN)6]4- 2 12 36 (Kr)
Fe 26 [Fe(CO)5] 0 10 36 (Kr)
Co 27 [Co(NH3)6]3+ 3 12 36 (Kr)
Ni 28 [Ni(CO)4] 0 8 36 (Kr)
Cu 29 [Cu(CN)4]3- 1 8 36 (Kr)
Pd 46 [Pd(NH3)6]4+ 4 12 54 (Xe)
Pt 78 [PtCl6]2- 4 12 86(Rn)

Fe 26 [Fe(CN)6]3- 3 12 35
Ni 28 [Ni(NH3)6]2+ 2 12 38
Pd 46 [PdCl4]2- 2 8 52
Pt 78 [Pt(NH3)4]2+ 2 8 84
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EAN violations
• [Ni(NH3)6]2+
• EAN = 28-2+12 = 38 # 36 (Kr)
• If we want 36 to be EAN we have to have penta coordination which
leads to an irregular structure

• Which in turn gives less stability

• Whenever higher coordination with a
regular structure is possible that is preferred

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Definition of Chelate
When more than one atom of the ligand is bonded to the central
metal atom, ring structures are formed. Such ring structured
complexes are called chelates.

[Co(NH3)6]Cl3 or [Pt(NH3)2Cl2]
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Example of Chelation
Chlorophyll, hemoglobin, vitamin B12 have porphyrin related
structures

chlorophyll hemoglobin vitamin B12

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Stability of Chelates
The chelates are more stable than the normal compounds.
Consider the following square planar complexes
Cu2+ + 2 (en)  [Cu(en)2]2+ (A)
Cu2+ + 4 NH3  [Cu(NH3)4]2+ (B)
• A and B have same 4 Cu-N bonds
The higher stability of A is due to
i) Two bonds have to be simultaneously broken to detach the ring.
More the rings are formed more will be the stability.
ii) Entropy factors (consider the backward reactions of the
reactions given above).
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Chelate formation: Major factor
[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en) [Ni(en)3]2+ + 6NH3
[Ni(H2O)6] + 6NH3 [Ni(NH3)6]2+ + 6H2O

 en and NH3 have similar N-donor environment

 en is bidentate and chelating ligand
 reaction proceeds towards right, G negative
 G = H - TS (H -ve, S ++ve)
 reaction proceeds due to entropy gain
 S ++ve is the major factor behind chelate effect
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No. of Chelate Ring

Stability increases because enthalpy becomes increasingly

negative (increased number of M–N bonds) & entropy increases
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Stability of complexes
[Fe(H2O)6]3+ + NCS-  [Fe(H2O)5(NCS)]2+ + H2O
Kf = [Fe(H2O)5(NCS)]2+/ [Fe(H2O)6]3+[NCS-]
Equilibrium constant Kf  formation constant
M + L  ML K1 = [ML]/[M][L]
ML + L  ML2 K2 = [ML2]/[ML][L]
ML2 + L  ML3 K3 = [ML3]/[ML2][L]

MLn-1 + L  MLn Kn = [MLn]/[MLn-1][L]

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Stability of complexes
• K1, K2….  Stepwise formation constant.
• To calculate concentration of the final product, use overall
formation constant n:

n = Kf = [MLn]/[M][L]n = K1 × K2 × K3 × …. × Kn

[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en) [Ni(en)3]2+ + 6NH3

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Isomerism
Coordination complexes:
Isomerism: Same atomic
composition, different structures

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Structural isomer

[CoBr(NH3)5]SO4 [Co(SO4)(NH3)5]Br
Ionization Isomers

[CrCl(H2O)5] Cl2 •H2O [CrCl2(H2O)4] Cl •2H2O

Hydrate Isomers

[Co(NH3)6][Cr(CN)6] [Cr(NH3)6][Co(CN)6]
[Cu(NH3)4][PtCl4] [Pt(NH3)4][CuCl4]
Coordination Isomers
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Structural isomer

Linkage Isomers

Ambidenate ligands
CN- through C or N;
SCN- through S or N;
S2O32- through S or O.
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Stereoisomers of square planer com.
[Ma2b2]
M=Metal centre;
a and b are monodentate ligands

[Ma2bc]
M=Metal centre;
a, b and c are monodentate ligands

[Mabcd]
M=Metal centre; a, b, c and d are
monodentate ligands
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Stereoisomers of Octahedral com.
[Ma3b3]

Facial isomer (fac) in which each set of three identical ligands

occupies one face of the octahedron surrounding the metal atom,
so that any two of these three ligands are mutually cis
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Stereoisomers of Octahedral com.
[Ma3b3]

Meridional isomer (mer) in which each set of three identical ligands

occupies a plane passing through the metal atom (the positions are
around the meridian of the octahedron)
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Stereoisomers of Octahedral com.
[M(AA)3]
M=Metal centre; AA is a symmetrical
bidentate ligand in which the two letters
A and A are indicating the two similar
coordinating atoms
Two Optical Isomers

[M(AB)3]
M=Metal centre; AB is an unsymmetrical
bidentate ligand in which the two letters A
and B are indicating the two different And their mirror images
coordinating atoms Total = 4 isomers
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Discussed topics……
 Double salt and coordination compound

 Werner’s work

 Identification of structure by isomer counting

 Effective atomic number

 Chelates and isomerism

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