GENERAL CHEMISTRY

Principles and Modern Applications TENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Complex Ions and

Coordination Compounds 24
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND
BIOCHEMISTRY

Slide 1 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

Complex Ions and CONTENTS
Coordination Compounds
24-1 Werner’s Theory of Coordination
Compounds: An Overview
24-2 Ligands

24-3 Nomenclature

24-4 Isomerism

24-5 Bonding in Complex Ions: Crystal Field

Theory
24-6 Magnetic Properties of Coordination
Compounds and Crystal Field Theory

24-7 Color and the Colors of Complexes

24-8 Aspects of Complex-Ion Equilibria

Slide 2 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

Complex Ions and CONTENTS
Coordination Compounds
24-9 Acid-Base Reactions of Complex Ions
24-10 Some Kinetic Considerations

24-11 Applications of Coordination

Chemistry

Slide 3 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 24-1 Werner’s Theory of Coordination
Compounds: An Overview

Compounds made up of simpler compounds are

called coordination compounds.
CoCl3 and NH3.
[Co(NH3)6]Cl3 and [CoCl (NH3)5]Cl2
Differing reactivity with AgNO3.

Alfred Werner (1866-

1919)

FIGURE 24-1
Two coordination compounds
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Two types of valence or bonding capacity.
Primary valence.
Based on the number of e- an atom loses in forming the ion.
Secondary valence.
Responsible for the bonding of other groups, called ligands,
to the central metal atom.

[Co(NH3)6]Cl3 → [Co(NH3)6]3+ + 3 Cl-

[CoCl(NH3)5]Cl2 → [CoCl(NH3)5]2+ + 2 Cl-

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 FIGURE 24-2
Structure of some complex ions

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 24-2 Ligands

Ligands are Lewis bases.

Donate electron pairs to metals.
Monodentate ligands.
Use one pair of electrons to form one point of
attachment to the metal ion.
Bidentate ligands.
Use two pairs of electrons to form two points of
attachment to the metal ion.
Tridentate, tetradentate…..polydentate

Slide 7 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 H H
- -
:

: Cl : :O H H N: CH3 N:
:

H H
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 ethylenediamine is a bidentate ligand

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Slide 10 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.
 FIGURE 24-3
Three representations of the chelate [Pt(en)2]2+

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 24-3 Nomenclature
Cation name comes first, followed by anion.
Anions as ligands are named by using the
ending –o.
Normally:
– ide endings change to –o.
– ite endings change to –ito.
– ate endings change to –ato.
Neutral molecules as ligands generally carried
the unmodified name.

Slide 12 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 The number of ligands of a given type is given by a
prefix.
Mono, di, tri, tetra, penta, hexa…
If the ligand name is a composite name itself:
Place it in brackets and precede it with a
prefix.
Bis, tris, tetrakis, pentakis...

Slide 13 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

Name the ligands first, in alphabetical order,
followed by the name of the metal center.
Prefixes are ignored in alphabetical order decisions.
The oxidation state of the metal center is given
by a Roman numeral.
If the complex is an anion the ending –ate is
attached to the name of the metal.

Slide 14 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 When writing the formula:
the chemical symbol of the metal is written first,

followed by the formulas of anions,

in alphabetical order.

and then formulas of neutral molecules,

in alphabetical order.

Slide 15 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 24-4 Isomerism
Isomers:
Differ in their structure and properties.
Structural isomers:
Differ in basic structure.
Stereoisomers:
Same number and type of ligands with the same
mode of attachment, but differ in the way the
ligands occupy space around the metal ion.

Slide 16 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

Ionization Isomerism

[CrSO4(NH3)5]Cl [CrCl(NH3)5]SO4
pentaaminsulfatochromium(III) chloride pentaaminchlorochromium(III) sulfate

Coordination Isomerism

[Co(NH3)6][CrCN6] [Cr(NH3)6][CoCN6]
hexaaminecobalt(III) hexacyanochromate(III) hexaaminechromium(III) hexacyanocobaltate(III)

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 Linkage Isomerism

Nitrite ion

FIGURE 24-4
Linkage isomerism illustrated
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 Geometric Isomerism

The geometric isomers of[PtCl2(NH3)2]

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 FIGURE 24-6
Cis and trans isomers of an octahedral complex

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 The geometric isomers of[PtCl3(NH3)3]

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 FIGURE 24-5
Geometric Isomerism - illustrated

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 Optical Isomerism

FIGURE 24-7
Superimposable and nonsuperimposable objects—an open-top box
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 FIGURE 24-8
Optical Isomers

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 dextrorotatory d-
levorotatory l-
FIGURE 24-9
Optical activity

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24-5 Bonding in Complex Ions:
Crystal Field Theory

Consider bonding in a complex to be an electrostatic

attraction between a positively charged nucleus and the
electrons of the ligands.
Electrons on metal atom repel electrons on ligands.
Focus particularly on the d-electrons on the metal ion.

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 FIGURE 24-11
Approach of six anions to a metal ion to form a complex ion with octahedral structure

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 FIGURE 24-12
Splitting of d energy levels in the formation of an octahedral complex ion

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 Spectrochemical series

Large Δ0
Strong field ligands

CN- > NO2- > en > py  NH3 > EDTA4- > SCN- > H2O >

ONO- > ox2- > OH- > F- > SCN- > Cl- > Br- > I-

Small Δ0
Weak field ligands

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E
N
E
R
G
Y

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 FIGURE 24-13
Crystal field splitting in a tetrahedral ion

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 FIGURE 24-14
Comparison of crystal field splitting in a square-planar and an octahedral complex

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 24-7 Color and the Colors of Complexes

Primary colors:
Red (R), green (G) and blue (B).
Secondary colors:
Produced by mixing primary colors.
Complementary colors:
Secondary colors are complementary to primary.
Cyan (C), yellow (Y) and magenta (M)
Adding a color and its complementary color
produces white.
Slide 33 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.
 FIGURE 24-16
The mixing of colors

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 Colored Solutions

FIGURE 24-17
Light absorption and transmission
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Slide 36 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.
 FIGURE 24-18
Effect of ligands on the colors of coordination compounds

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 24-8 Aspects of Complex-Ion Equilibria

Zn2+(aq) + 4 NH3(aq) → [Zn(NH3)4]2+(aq)

[[Zn(NH3)4]2+]
Kf = = 4.1108
[Zn2+][NH3]4
Displacement is stepwise from the hydrated ion:
Step 1:
[Zn(H2O)4]2+(aq) + NH3(aq) [Zn(H2O)3(NH3)]2+(aq) + H2O(aq)

[[Zn(H2O)3(NH3)]2+]
K1= = 1 = 3.9102
[[Zn(H2O)4]2+][NH3]

Slide 38 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 24-8 Aspects of Complex-Ion Equilibria
Step 2:
[Zn(H2O)3(NH3)]2+(aq) + NH3(aq) [Zn(H2O)2(NH3)2]2+(aq) + H2O(aq)

[[Zn(H2O)2(NH3)2]2+]
K2 = = 2.1102
[[Zn(H2O)3(NH3)]2+][NH3]
Combining steps 1 and 2:
[Zn(H2O)4]2+(aq) + 2 NH3(aq) [Zn(H2O)2(NH3)2]2+(aq) + 2 H2O(aq)

[[Zn(H2O)2(NH3)2]2+]
K = 2 = = K1  K2 = 2 = 8.2104
[[Zn(H2O)4]2+][NH3]2

Slide 39 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 4 = K1  K2  K3  K4 = Kf

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 24-9 Acid-Base Reactions of Complex Ions

FIGURE 24-19
Ionization of [Fe(H2O)6]3+
Slide 41 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.
 Expressed in a chemical equation:

[Fe(H2O)6]3+(aq) + H2O(aq) [Fe(H2O)5(OH)]2+(aq) + H3O+(aq)

Ka1 = 9x10-4

[Fe(H2O)5(OH)]2+ (aq) + H2O(aq) [Fe(H2O)4(OH)2]2+(aq) + H3O+(aq)

Ka2 = 5x10-4

Slide 42 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 24-10 Some Kinetic Considerations

fast [Cu(H2O)4]2+ + 4 NH3 → [Cu(NH3)4]2+ + 4 H2O

fast [Cu(H2O)4]2+ + 4 Cl- → [Cu(Cl)4]2- + 4 H2O

Water is said to be a labile ligand.

Slow reactions (often monitored by color change) are

caused by non-labile ligands.
Fast reactions can operate at the diffusion limit.

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 FIGURE 24-20
Labile complex ions

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 FIGURE 24-21
Inert complex ions

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 24-11 Applications of Coordination Chemistry

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 Stabilization of Oxidation States

Co3+(aq) + e- → Co2+(aq) E° = +1.82 V

4 Co3+(aq) + 2 H2O(l) → 4 Co2+(aq) + 4 H+ + O2(g)

E°cell = +0.59 V
But:
Co3+(aq) + NH3(aq) → [Co(NH3)6]2+(aq) Kf = 4.51033
and
[Co(NH3)6]3+(aq) + e- → [Co(NH3)6]2+(aq) E° = +0.10 V

Slide 47 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.

 Photography: Fixing a Photographic Film
Black and white.
Finely divided AgBr on modified cellulose.
Photons oxidize Br- to Br and reduce Ag+ to Ag.
Hydroquinone (C6H4(OH)2) developer:
Reacts only at the latent image site where some
Ag+ is present and converts all Ag+ to Ag.
Negative image.
Fixer removes remaining AgBr.
AgBr(s) + 2 S2O32-(aq) → [Ag(S2O3)2]3-(aq) + Br-(aq)

Print the negative

Slide 48 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.
 Qualitative Analysis

Add F- to
In the
sequester
presence of
the Fe3+
trace Fe3+
and prevent
interference
.
[Co(SCN)4]2- [Fe(SCN)(H2O)5]2+ [Co(SCN)4]2-
[FeF6]3-
FIGURE 24-22
Qualitative tests for Co2+ and Fe3+
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 Sequestering Metal Cations

tetrasodium EDTA

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 FIGURE 24-23
Structure of a metal-EDTA complex

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 Biological Applications: Porphyrins

FIGURE 24-24 FIGURE 24-25

The porphyrin structure Structure of chlorophyll a

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 End of Chapter Questions

Break problems down into managable pieces.

Solve each zone “independently”.
Iterate as information from one zone moves
back into another.
Effective use of variables is important.

Slide 53 of 53 General Chemistry: Chapter 24 Copyright © 2011 Pearson Canada Inc.