Lecture 1

CHM102A_2020
Gurunath Ramanathan

gurunath@iitk.ac.in
+7417
 Important notes
• Mid semester exam attendance is important. Otherwise- the
instructor drops you from this course.
• No makeup for quizzes. But makeup examination for midsem and
endsem allowed if it is for medical reasons and approved by
SUGC.
• Cheating in examinations/ quizzes will attract a “F” grade.
• Switch off the mobiles during class.
• Use Pingala to find your tutorial groups.
• Be seated before the second bell.
• Doubts can be posted in the CHM102A_2020 telegram discussion
group.
Meet your tutors
 Revision of some concepts
• What are complexes?
• What is a coordination compound?
• How are coordination compounds different from double
salts?
• Nomenclature
• Isomerism
• D- block elements
• Do I need to remember the periodic table/ other basic
concepts? – yes & one will be provided
 Addition compound versus complexes

Mohr’s salt, Carnalite Prussian blue,

Potash alum Fe-Heme in hemoglobin
Double salts are true to their constituent ions-
while complexes behave very differently.
They lose their identity in solution

complex salts retain their identity in solution

• Components of a coordination compound
– Complex ion (enclosed in square barckets)

– Counter ions
– Some coordination compounds do not contain
a complex ion

– Most of the metals in complexes are transition

metals

Copyright McGraw-Hill 2009 7

The Position of the Transition Elements on the
Periodic Table
20_432

d-block transition elements

Sc Ti V Cr Mn Fe Co Ni Cu Zn

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

La* Hf Ta W Re Os Ir Pt Au Hg

Ac† Unq Unp Unh Uns Uno Une Uun Uuu

f-block transition elements

*Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

† Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Multiple Oxidation States
 19.1 Coordination complexes

The electronic basis of the color of metal complexes

13
Coordination complex: A structure containing a metal (usually a metal ion) bonded
(coordinated) to a group of surrounding molecules or ions.

Ligand (ligare is Latin, to bind): A ligand is a molecule or ion that is directly

bonded to a metal ion in a coordination complex

A ligand uses a lone pair of electrons (Lewis base) to bond to the metal
ion (Lewis acid)

Coordination sphere: A metal and its surrounding ligands

Note: religare is Latin, to bind tightly

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 Alfred Werner: the father of the structure of
coordination complexes

The Nobel Prize in Chemistry 1913

"in recognition of his work on the linkage
of atoms in molecules by which he has
thrown new light on earlier investigations
and opened up new fields of research
Alfred Werner especially in inorganic chemistry"
Switzerland
University of Zurich
Zurich, Switzerland
b. 1866
(in Mulhouse, then Germany)
d. 1919
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Werner’s explanation of coordination complexes
Metal ions exhibit two kinds of valence

The primary valence is the oxidation number (positive

charge) of the metal (usually 2+ or 3+)

The secondary valence is the number of atoms that are

directly bonded (coordinated) to the metal

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 Coordination sphere and coordination number

• Metal and ligands bound to it

• Determined by number of donor atoms directly bonded to metal

• Most common 2,4,6
• Larger ligands favor lower coordination number
• Ligands that donate negative charge easily also favor low cn
 Example of a coordination complex: [Co(NH3)6]Cl3

What is the atomic composition of [Co(NH3)6]Cl3

the complex?

What is the net charge of the [Co(NH3)6]3+

complex?

3+ is required to balance the three Cl-

How do we know the charge ions
is 3+ on the metal?

The primary valence of [Co(NH3)6]Cl3 is 3 or

charge on Co is 3+ or Co(III)
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The secondary valence of [Co(NH3)6]Cl3 is 6 (cn/ligands)
 19.2 Structures of Coordination Complexes: The ammonia
complexes of Co(III) = Co3+

How did Werner deduce the structure of coordination complexes?

Composition Ions released Color

CoCl3.6NH3 3 “free” Cl- ions Orange-Yellow

CoCl3.5NH3 2 “free” Cl- ions Purple

CoCl3.4NH3 1 “free” Cl- ions Green

CoCl3.3NH3 0 “free” Cl- ions Green

In all of these complexes there is no free NH3

(No reaction with acid) 19
 Classification of Ligands
• Monodentate
– CO

• Bidentate
– bipyridyl

• Hexadentate
– EDTA
Complex of Ca2+-ethylenediaaminetetraacetate
 Logic: Cl- is not in coordination sphere; NH3 is in sphere

Compound 1: CoCl3.6NH3 = [Co(NH3)6]3+(Cl-)3 = [Co(NH3)6](Cl)3

Conclude: 3 free Cl- ions, [Co(NH3)6]3+

Compound 2: CoCl3.5NH3 = [Co(NH3)5Cl]2+(Cl-)2 = [Co(NH3)5Cl](Cl)2

Conclude: 2 free Cl- ions, [Co(NH3)5Cl]2+

Compound 3: CoCl3.4NH3 = [Co(NH3)4Cl2]1+(Cl-) = [Co(NH3)4Cl2](Cl)

Conclude: 1 free Cl- ion, [Co(NH3)4Cl2]1+

Compound 4: CoCl3.3NH3 = [Co(NH3)3Cl3]

No free Cl- ions 21

 Nomenclature of Complexes
• The cation is named before the anion
• When naming a complex
– Ligands are named first in alphabetical order
– Metal atom/ion is named last with its oxidation state given as
Roman numerals in parenthesis
– Use no space in complex name - self study/ tutorial
 Isomerism in Complexes
• Complexes are notorious for showing different types of
isomerism
– Constitutional isomers
-Linkage and Ionization isomers
– Stereoisomers
Geometric isomers (diastereomers) and enantiomers,
Hydrate isomers:

Water in outer sphere (water that is part of

solvent)

Water in the inner sphere water (water is a

ligand in the coordination sphere of the metal)

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 Linkage isomers

Bonding to metal may occur at the S or the N atom

Bonding occurs from

N atom to metal

Bonding occurs from

S atom to metal

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Stereoisomers: geometric isomers (cis and trans)

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Nonsuperimposable Mirror Images: A Chemical Example

27
Copyright McGraw-Hill 2009
 Optical isomers: enantiomers

Enantiomers are mirror images which are not superimposable

Enantiomers do not have a plane of symmetry

Any molecule which possesses a plane of symmetry is superimposable on its

mirror image

Enantiomers rotate polarized light in different directions; therefore, enanotiomers

are also termed “optical isomers”

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 Enantiomers: non superimposable mirror images

A structure is termed chiral if it is not superimposable on its mirror image

Structure Mirror image

Two chiral structures: non superimposable mirror images

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EDTA complexes are optically active

30
Which are enantiomers (non-superimposable mirror images) and which are identical
(superimposable mirror images)?

31
 Why do we need to eat transition metals?
Some critical enzymes in our cells are metalloproteins, giant
biomolecules which contain a metal atom

Hemoglobin is a metalloprotein which contains an iron atom

and transports O2 through out living systems

Vitamin B12, which prevents pernicious anemia, contains

a Co atom which gives the vitamin a deep red color

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 Crystal Field Theory
Van Vleck and Bethe

• Crystal Field Theory

– Model for bonding in transition metal
1967
complexes
• Accounts for observed properties of transition
metal complexes
1977
– Focuses on d-orbitals
– Ligands = point negative charges
– Assumes ionic bonding
• electrostatic interactions
Shapes of orbitals
 dxz dxy dyz
dx2-y2

For each, the yellow zones are

where the wave functions have
negative values and the blue zones
denote positive values.

dz2
 Crystal Field Theory
Bethe/van Vleck
• Electrostatic Interactions
– (+) metal ion attracted to (-) ligands (anion or
dipole)
• provides stability
– lone pair e-’s on ligands repulsed by e-’s in
metal d orbitals
• interaction called crystal field
• influences d orbital energies
– not all d orbitals influenced the same way
 Crystal Field Theory

Octahedral Crystal Field -

(-) Ligands attracted to (+) metal
ion; provides stability
- -
+
- -

-
d orbital e-’s repulsed by (–) ligands; increases
d orbital potential energy

ligands approach along x, y, z axes

 Crystal Field Theory
• Basis: purely electrostatic interaction
• Spherical field: d orbitals degenerate
spherical field

free ion
What will happen when six ligands •
approach from the six vertices of •
an octahedron?
•
•

•
•
 metal ion in octahedral
octahedral crystal field complex

d orbital energy levels dz2 dx2- y2

_ _

_____
3/5
DO
_ _2/5 _
E
dxy dxz dyz

_ _ isolated
_ _ _metal ion Metal ion and the nature of the ligand
determines D
d-orbitals
Crystal Field Theory

eg t2g
Crystal Field Theory

eg t2g

eg

crystal field stabilization

energy (CFSE)

t2g
Crystal Field Theory

eg

crystal field stabilization

energy (CFSE)

t2g
 Crystal Field Theory
• Distribution of electrons
d2 d3

How is a d4 configuration distributed?

Crystal Field Theory

Pairing energy (P) vs. DO

• If DO < P, weak field;
e.g., [Cr(OH2)6]2+

• If DO > P, strong field;

e.g., [Cr(CN)6]4–
 Crystal Field Theory
• Tetrahedral field

t2

t2
e

e
 Crystal Field Theory
• Square planar field

DSP
Crystal Field Theory
Factors affecting magnitude of D
1. Oxidation state of the metal ion
2. Nature of the metal ion
3. Number and geometry of the ligands
4. Nature of the ligands
 Crystal Field Theory
• Ligands are point charges
• Metal d electrons repel ligands
• Splitting of d orbitals
• Explanation for colors and magnetism of complex ions
• No hybridization required