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General Chemistry (CHEMF111)

Tutorial 1: Coordination Compounds

Course Handout
Course No. : CHEM F111
Course Title : GENERAL CHEMISTRY
Scope and Objective of the Course: The course provides a
comprehensive survey of the concepts involved in the study of the
transition metal coordination complexes, VB and CFT for inorganic
complexes, stereochemistry and reactivity of organic compounds,
electronic structure of atoms and molecules, spectroscopy, chemical
equilibrium, chemical kinetics,
Text Books:
T1: P.W. Atkins, Elements of Physical Chemistry: 6th Edition, Oxford
University Press, 2015.
T2: T. W. Graham Solomons and Craig B. Fryhle, Organic Chemistry,
10th Edition, John Wiley & Sons, Inc. New York, 2011.
T3: J. D. Lee, Concise Inorganic Chemistry, 5th Edition, Blackwell
Science, Oxford, 1999.

Course Handout
First ~7 Lectures will be on Inorganic
Chemistry: Coordination Compounds
Next ~8-20 Lectures will be on Organic
Chemistry: Stereochemistry, Substitution,
Elimination, Addition, Aromaticity.
Physical Chemistry: ~21 Lectures: Quantum
Theory, Atomic Structure, Chemical Bonding,
Spectroscopy, Thermodynamics and Chemical
Kinetics.

Course Handout
Evaluation Scheme:
Component
Test I

Duration Weightage
Date, Day &Time
%
20/09/16, Tuesday
60 min
30%
2.00 pm-3.00 pm

Remarks
Closed Book

Test II

60 min

30%

25/10/16, Tuesday
2.00 pm-3.00 pm

Comprehensive
Examination

3 hrs.

40%

05/12/16, Monday Closed Book


(FN: 9.00 am- 12.00
pm)

Open Book

Coordination Compounds
To explain
Structure
Color
and Magnetic properties of Transition metal
compounds using concepts of Valence Bond
Theory (VBT) and Crystal Field Theory (CFT)

Coordination Compounds:
Problem I: Identifying Primary and
secondary valency

Example: Identify primary and secondary


valency in the following compounds.
CoCl2, [Co(NH3)6]Cl3
Number of Charges and Particles:
Conductivity Measurements
Cryoscopic Measurements

Problem II: Identifying structure through


Cryoscopic and Conductivity
measurements
FORMULA

CRYOSCOPIC
MEASUREMENT

MOLAR
CONDUCTIVITY

STRUCTURE

CoCl3.6NH3
CoCl3.5NH3

4
3

6
4

?
?

CoCl3.4NH3
2
CoCl3.3NH3
1
Co(NO2)3.KNO2.2NH3 2

2
0
2

?
?
?

Problem III: Calculation of Effective atomic numbers


of some metals in complexes. Fill up the boxes with
question marks
Atom

Atomic Complex
number

Electrons Electrons
EAN
lost in ion gained by
formation coordination

Cr

24

[Cr(CO)6]

36 (Kr)

Fe

26

[Fe(CN)6]4-

12

36 (Kr)

Fe

26

[Fe(CO)5]

10

36 (Kr)

Co

27

[Co(NH3)6]3+

36 (Kr)

Ni

28

[Ni(CO)4]

36 (Kr)

Cu

29

[Cu(CN)4]3-

Pd

46

[Pd(NH3)6]4+

12

54 (Xe)

Pt

78

[PtCl6]2-

12

Fe

26

[Fe(CN)6]3-

12

Ni

28

[Ni(NH3)6]2+

12

Pd

46

[PdCl4]2-

52

Pt

78

[Pt(NH3)4]2+

84

(Kr)

(Rn)

Problem IV: Isomers

Only one form


e.g., [Pt(NH3)5Cl]3+
[Co(NH3)5Cl]2+

Only one form


e.g., [Co(NH3)6]3+
[Fe(CN)6]3-

Isomers in octahedral complexes


MX4E2

Trans isomer

Cis isomer
Examples:
[Pt(NH3)4Cl2]2+,
[Co(NH3)4Cl2]+

Isomers in octahedral complexes


MX3E3

Meridianal

Facial

Isomers in octahedral complex, MX5E

All corners of a regular octahedron are equivalent. How many isomers?

Isomers in octahedral complex, MX4E2

Label the two structures above as cis- or trans-?

Isomers in octahedral complex, MX3E3

Label the two structures above as facial or meridianal?

Isomers in square planar complexes


Cis

Trans

Example: Pt(NH3)2Cl2

Optical isomers

Example : [Co(en)3]n+ , nonsuperposable mirror images

[Co(en)]33+

Coordination complex: Cis and trans


isomers

Example of complex with polydentate ligand:


[Co(EDTA)]-

Problem V: Denticity of Ligands-Examples

Problem VI: VBT


Formation of an Inner orbital Co3+
Octahedral complex.

3d

4s

4p

d2sp3hybridization
Octahedral shape
Inner orbital complex
Low spin complex
Type of question: Using VBT theory diamagnetic or paramagnetic
nature of a octahedral coordination complex

4d

VBT (Contd.)
Formation of a tetrahedral complex from
d6 system
3d

4s
4p
sp3hybridization
Tetrahedral shape
Outer orbital complex
High spin complex

Type of question: Using VBT theory explain magnetic property


of a tetrahedral coordination complex

4d

Problem VII: Arrange the following ligands in the increasing


order of their strength

CO, CN- , I- , EDTA4-, o-phenanthroline, Cl-

Weak field ligands -> Strong field ligands


I- < Br- < S2- < Cl- < NO3-< F- < OH- < EtOH < Oxalate < H2O <
EDTA4- < (NH3 and pyridine) < ethylenediamine < dipyridyl < ophenanthroline < NO2- < CN- < CO

Color Wheel

Problem VIII: Crystal Field Theory


Crystal field splitting by various ligands
Complex

Absorption (cm-1) Absorption


(kJ/mol)

[CrCl6]3-

13640

163

[Cr(H2O)6]3+

17830

[Cr(NH3)6]3+

21680

259

[Cr(CN)6]3-

26280

Draw the crystal field splitting of d-orbitals and


calculate CFSE for above coordination complexes

Problem IX: Crystal Field Theory


Account for the following observation
using CFT
Complex

kJ/mol

[Co(NH3)6]3+

24800

296

[Rh(NH3)6]3+

34000

406

[Ir(NH3)6]3+

41000

490

Problem X: CFT: Pairing energy vs 0


CFSE and pairing energies of some complexes:
Complex

Config. 0 (cm-1)

P (cm-1)

Predicted

Found

[Fe(H2O)6 ]2+

d6

10400

17600

High
spin

[Fe(CN)6 ]4-

d6

32850

17600

Low
spin

[CoF6 ]3-

d7

13000

21000

High
spin

[Co(NH3)6 ]3+

d7

23000

21000

Low
spin

Question: What is the trend in P down the group of


transition metals?, and for 0 ?

Problem XI: In which of the following complexes P should


be added to CFSE?

Electronic
configuration

CFSE

d1

-0.4 0

d2

-0.8 0

d3

-1.2 0

d4 (High spin)

-1.2 0 + 0.6 0

d4 (Low spin)

-1.6 0

The CFSE of d4 (Low spin) is higher than d4 (High spin),


but for the low spin complex the pairing energy P (Total
stabilization = -1.6 0 + P) should be added to CFSE to
get total stabilization energy.

Problem XII: Calculation of CFSE, electronic arrangements and


magnetic moment in octahedral and tetrahedral complexes
No. of d- t2g
electrons

eg

CFSE

t2g

eg

CFSE

-0.4

1.73 1

-0.4

1.73

-0.8

2.83 2

-0.8

2.83

-1.2

3.87 3

-1.2

3.87

-0.6

4.90 4

-1.6

2.83

5.92 5

-2.0

1.73

-0.4

4.90 6

-2.4

-0.8

3.87 6

-1.8

1.73

-1.2

2.83 6

-1.2

2.83

-0.6

1.73 6

-0.6

1.73

10

CFSE (Octahedral) = (-0.4 nt2g + 0.6 neg) o

Problem XIII: CFSE: Tetrahedral Complexes

t = (4/9)O
(Tetrahedral
CFSE scaled
for
comparison
with
octahedral
values)

Weak
field
(Oct.)

Strong
field
(Oct.)

1.73

-0.6

-0.27

-0.4

-0.4

d2

2.83

-1.2

-0.53

-0.8

-0.8

d3

3.87

-0.8

-0.36

-1.2

-1.2

d4

4.90

-0.4

-0.18

-0.6

-1.6

d5

5.92

d6

4.90

d7

d8

d9

d10

No. of delectrons

d1

t2

Symmetrical electronic arrangements


Electronic
t2g
configuration

eg

Nature of
ligand field

Examples

d0

Strong or
weak

TiO2, [TiF6]2-, [TiCl6]2-

d3

Strong or
weak

[Cr(Ox)3]3-, [Cr(H2O)6]3+

d5

Weak

[MnF6]4-, [FeF6]3-

d6

Strong

[Fe(CN)6]4-, [Co(NH3)6]3+

d8

Weak

[NiF6]4-, [Ni(H2O)6]2+

d10

Strong or
weak

[Zn(NH3)6]2+,
[Zn(H2O)6]2+

Asymmetrical electronic arrangements


Electronic
t2g
configuration

eg

Nature of
ligand field

Examples

d4

Weak (HS)

Cr(II), Mn(III)

d7

Strong (LS)

Co(II), Ni(III)

d9

Strong or
weak

Cu(II)

The two eg orbitals are normally degenerate.


Asymmetric filling lead to degeneracy being destroyed.
If the electron is present in dz2 orbital,
the ligands approaching along +z or z
Will encounter greater repulsion than other four ligands.
(Tetragonal elongation)

P9: Draw the d-orbital splitting pattern, if ligands are


elongated or compressed along z-axis

P14: Jahn-Teller Distortion


Electronic
t2g
configuration

eg

Nature of
ligand field

Examples

d4

Weak (HS)

Cr(II), Mn(III)

d7

Strong (LS)

Co(II), Ni(III)

d9

Strong or
weak

Cu(II)

The two eg orbitals are normally degenerate.


Asymmetric filling lead to degeneracy being destroyed.
If the electron is present in dz2 orbital,
the ligands approaching along +z or z
Will encounter greater repulsion than other four ligands.
(Tetragonal elongation)

Jahn-Teller Distortion: Elongation along zaxis


d (x2-y2)

d (z2)

d (xy)

d (xz) d (yz)
Question: Draw the splitting pattern if ligands are compressed along z-axis

P15: Square Planar Coordination


Question: Write down 2
examples of coordination
complexes that would
exhibit square planar
coordination

dx2-y2

dxy

d-orbital
splitting in
square planar
coordination

dz2
dxz dyz

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