Chemistry of Coordination

Compounds

Chemistry of
Coordination
Compounds
1
Chemistry of
Coordination
Compounds
2
Chemistry of
Coordination
Compounds
3
Χ = magnetic susceptibility g = spin of electron
T = Temperature S = No. of unpaired spin
L = orbital angular momentum
Chemistry of
Coordination
Compounds
4
Chemistry of
Coordination
Compounds
5
Chemistry of
Coordination
Compounds
6
Chemistry of
Coordination
Compounds
7
Chemistry of
Coordination
Compounds
8
Chemistry of
Coordination
Compounds
9
Chemistry of
Coordination
Compounds
10
Chemistry of
Coordination
Compounds
11
Chemistry of
Coordination
Compounds
12
Chemistry of
Coordination
Compounds
13
Chemistry of
Coordination
Compounds
14
Chemistry of
Coordination
Compounds
15
Chemistry of
Coordination
Compounds
16
Chemistry of
Coordination
Compounds
17
Chemistry of
Coordination
Compounds
18
Chemistry of
Coordination
Compounds
19
Chemistry of
Coordination
Compounds
20
Chemistry of
Coordination
Compounds
21
Chemistry of
Coordination
Compounds
22
Chemistry of
Coordination
Compounds
23
Chemistry of
Coordination
Compounds
24
Chemistry of
Coordination
Compounds
25
Chemistry of
Coordination
Compounds
26
Chemistry of
Coordination
Compounds
27
Figure 23.13
Hybrid orbitals and bonding in the octahedral [Cr(NH3)6]3+ ion.

Chemistry of
Coordination
Compounds
28
Figure 23.14

Hybrid orbitals and bonding in the square planar [Ni(CN)4]2- ion.

Chemistry of
Coordination
Compounds
29
Figure 23.15
Hybrid orbitals and bonding in the tetrahedral [Zn(OH)4]2- ion.

Chemistry of
Coordination
Compounds
30
 Metal complexes and color

The ligands of a metal complex effect its color

Chemistry of
Coordination
Addition of NH3 ligand to Cu(H2O)4 changes its color Compounds
31
Chemistry of
Coordination
Compounds
32
Chemistry of
Coordination
Compounds
33
Chemistry of
Coordination
Compounds
34
Chemistry of
Coordination
Compounds
35
Figure 23.17 The five d-orbitals in an octahedral field of ligands.

Chemistry of
Coordination
Compounds
36
Ligands will interact with some d orbitals more than others

Depends on relative orientation of orbital and ligand

Ligands point right at lobes

Chemistry of
Coordination
Compounds
37
In these orbitals, the ligands are between the lobes
Interact less strongly

Chemistry of
Coordination
Compounds
38
Figure 23.18 Splitting of d-orbital energies by an octahedral field
of ligands.

Chemistry of
D is the splitting energy Coordination
Compounds
39
Figure 23.19 The effect of the ligand on splitting energy.

Chemistry of
Coordination
Compounds
40
 Figure 23.22 The spectrochemical series.

•For a given ligand, the color depends on the oxidation state of the metal ion.

•For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

SMALLER D LARGER D

LONGER  SHORTER 

Chemistry of
Coordination
Compounds
41
Sample Problem 23.5 Ranking Crystal Field Splitting Energies for
Complex Ions of a Given Metal

PROBLEM: Rank the ions [Ti(H2O)6]3+, [Ti(NH3)6]3+, and [Ti(CN)6]3- in terms of

the relative value of D and of the energy of visible light absorbed.

PLAN: The oxidation state of Ti is 3+ in all of the complexes so we are

looking at the crystal field strength of the ligands. The stronger the
ligand the greater the splitting and the higher the energy of the light
absorbed.

SOLUTION: The field strength according to is CN- > NH3 > H2O. So
the relative values of D and energy of light absorbed will be

[Ti(CN)6]3- > [Ti(NH3)6]3+ > [Ti(H2O)6]3+

Chemistry of
Coordination
Compounds
42
Figure 23.23 High-spin and low-spin complex ions of Mn2+.

Chemistry of
Coordination
Compounds
43
Chemistry of
Coordination
Compounds
44
Chemistry of
Coordination
Compounds
45
Different ligands interact more or less, change E spacing
Of D orbitals.

Chemistry of
Coordination
Compounds
46
Spectrochemical series (strength of ligand interaction)
Increasing D

Cl- < F- < H2O < NH3 < en < NO2- < CN-

Increasing D

Chemistry of
Coordination
Compounds
47
Electron configurations of some octahedral complexes

Chemistry of
Coordination
Compounds
48
As Energy difference increases, electron configuration
changes
“Low spin”
“High spin”

Co(III) is d6 Chemistry of
Coordination
Compounds
49
Chemistry of
Coordination
Compounds
50
Figure 23.24 Orbital occupancy for high-spin and low-spin
complexes of d4 through d7 metal ions.

high spin: low spin: high spin: low spin:

weak-field strong-field weak-field strong-field
ligand ligand ligand ligand

Chemistry of
Coordination
Compounds
51
 Why does anything have color?

Light of different frequencies give different colors

We learned that elements can emit light of different
frequency or color.
But these coordination complexes are not emitting light
Chemistry of
They absorb light. Coordination
Compounds
52
How does that give color?
 Chemistry of
= 495 nm Coordination
Compounds
53
Figure 23.20 The color of [Ti(H2O)6]3+.

Chemistry of
Coordination
Compounds
54
Figure 23.21 Effects of the metal oxidation state and of ligand
identity on color.

[V(H2O)6]2+ [V(H2O)6]3+

[Cr(NH3)6]3+ [Cr(NH3)5Cl ]2+

Chemistry of
Coordination
Compounds
55
Chemistry of
Coordination
Compounds
56
Chemistry of
Coordination
Compounds
57
Chemistry of
Coordination
Compounds
58