Coordination Chemistry

Chemistry
Third Edition
Julia Burdge
Lecture PowerPoint
Chapter 22
Coordination Chemistry
Copyright © 2012, The McGraw-Hill Compaies, Inc. Permission required for reproduction or display.
Coordination Chemistry
CHAPTER 22
22.1 Coordination Compounds
22.2 Structure of Coordination Compounds
22.3 Bonding in Coordination Compounds: Crystal Field
Theory
22.4 Reactions of Coordination Compounds
22.5 Applications of Coordination Compounds
2
Topics
Properties of Transition Metals
Ligands
Nomenclature of Coordination Compounds
3

Coordination compounds contain coordinate covalent bonds
formed by the reactions of metal ions with groups of anions
or polar molecules.
A coordinate covalent bond is a covalent bond in which one of

the atoms donates both of the electrons that constitute the
bond.
A coordination compound often consists of a complex ion and

one or more counter ions.
4

Use square brackets to separate the complex ion from the
counter ion.
Most of the metals in coordination compounds are transition

metals.
5

Transition metals (green) have incompletely filled d subshells
or form ions with incompletely filled d subshells.
6

The Group 2B metals—Zn, Cd, and Hg — are d-block metals,
but they are not transition metals.
Incompletely filled d subshells give rise to several properties:

• distinctive colors
• formation of paramagnetic compounds
• catalytic activity
• tendency to form complex ions
7

The most common transition metals are Sc through Cu.
8

Transition metals have
• higher densities
• higher melting points and boiling points
• higher heats of fusion and vaporization
than the main group and Group 2B metals
9

Transition metals exhibit variable oxidation states.
All these metals can exhibit

the oxidation state +3 and
nearly all can exhibit the
oxidation state +2.
The highest oxidation state for

a transition metal is +7.
10
Ligands
The molecules or ions that surround the metal in a complex
ion are called ligands.
To be a ligand, a molecule or ion must have at least one

unshared pair of valence electrons.
Examples include:
11
Ligands
The ligand acts as a
Lewis base while the
transition metal acts
as a Lewis acid.
12
Ligands
The atom in a ligand that is bound directly to the metal atom
is known as the donor atom.
Nitrogen is the
donor atom in the
[Cu(NH3)4]2+
complex ion.
13
Ligands
The coordination number in a coordination compound refers
to the number of donor atoms surrounding the central metal
atom in a complex ion.
The coordination number of Cu2+ in [Cu(NH3)4]2+ is 4.
The most common coordination numbers are 4 and 6.
14
Ligands
Depending on the number of donor atoms a ligand possesses,
it is classified as
• monodentate (1 donor atom)
• bidentate (2 donor atoms)
• polydentate (> 2 donor atoms)
Ethylenediamine
forms two bonds to
a metal atom
(bidendate).
15
Ligands
Bidentate and polydentate ligands are also called chelating
agents because of their ability to hold the metal atom like a
claw.
EDTA is a
polydentate ligand ‒
6 donor atoms.
16
Ligands
The oxidation state of a transition metal in a complex ion is
determined using the known charges of the ligands and the
known overall charge of the complex ion.
In the complex ion [PtCl6]2‒, each chloride ion ligand has an

oxidation number of ‒1.
For the overall charge of the ion to be ‒2, the Pt must have an
oxidation number of +4.
17
SAMPLE PROBLEM 22.1
Determine the oxidation state of the central metal atom in
each of the following compounds:
(a) [Ru(NH3)5(H2O)]Cl2
(b) [Cr(NH3)6](NO3)3
(c) Fe(CO)5
18
SAMPLE PROBLEM 22.1
Setup
a) The complex ion is [Ru(NH3)5(H2O)]2+. Each ligand is

neutral.
b) The complex ion is [Cr(NH3)6]3+. Each ligand is neutral.
c) Fe(CO)5 does not contain a complex ion. The ligands are

CO molecules, which have a zero charge.
19
SAMPLE PROBLEM 22.1
Solution
a) [Ru(NH3)5(H2O)]Cl2 +2
b) [Cr(NH3)6](NO3)3 +3
c) Fe(CO)5 0
20

The rules for naming ionic coordination compounds are as
follows:
1. The cation is named before the anion. The rule holds

regardless of whether the complex ion bears a net positive
or a net negative charge.
2. Within a complex ion, the ligands are named first, in

alphabetical order, and the metal ion is named last.
21

3. The names of anionic ligands end with the letter o,
whereas neutral ligands are usually called by the names of
the molecules. The exceptions are H2O (aqua), CO
(carbonyl), and NH3 (ammine).
4. When two or more of the same ligand are present, use

Greek prefixes di, tri, tetra, penta, and hexa, to specify
their number.
22

5. The oxidation number of the metal is indicated in Roman
numerals immediately following the name of the metal.
6. If the complex is an anion, its name ends in –ate.
23
24
25
SAMPLE PROBLEM 22.2
Write the names of the following coordination compounds:
(a) [Co(NH3)4Cl2]Cl
(b) K3[Fe(CN)6]
26
SAMPLE PROBLEM 22.2
Setup
a) The cation is a complex ion with a charge of +1. The
counter ion is Cl‒. The oxidation state of cobalt +3.
b) The cation is K+, and the anion is a complex ion with a

charge of ‒3. The oxidation state of iron +3.
Solution
a) [Co(NH3)4Cl2]Cl Tetraamminedichlorocobalt(III) chloride
b) K3[Fe(CN)6] Potassium hexacyanoferrate(III)
27
SAMPLE PROBLEM 22.3
Write formulas for the following compounds:
(a) pentaamminechlorocobalt(III) chloride
(b) dichlorobis(ethylenediamine)platinum(IV) nitrate
28
SAMPLE PROBLEM 22.3
Setup
a) There are five NH3 molecules and one Cl‒ ion. The overall
charge on the complex ion +2. There are two chloride ions
as counter ions.
b) There are two bidentate ethylenediamines and two Cl‒

ions. The overall charge on the complex ion +2. There are
two nitrate ions as counter ions.
29
SAMPLE PROBLEM 22.3
Solution
a) [Co(NH3)5Cl]Cl2 (pentaamminechlorocobalt(III) chloride)
b) [Pt(en)2Cl2](NO3)2
(dichlorobis(ethylenediamine)platinum(IV) nitrate)
30
Topics
Structure of Coordination Compounds
31
32

Compounds in which ligands are arranged differently around
the central atom are known as stereoisomers.
Stereoisomers have distinctly different physical and chemical

properties.
Coordination compounds may exhibit two types of

stereoisomerism: geometric and optical.
33

Geometrical isomers are stereoisomers that cannot be
interconverted without breaking chemical bonds.
Geometric isomers come in pairs: cis and trans.
Cis means that two particular atoms are adjacent to each

other.
Trans means that the atoms are on opposite sides in the

structural formula.
34

The cis and trans isomers generally have different colors,
melting points, dipole moments, and chemical reactivities.
35
36

Optical isomers are nonsuperimposable mirror images.
Optical isomers also come in pairs.
The optical isomers of a compound have identical physical

and chemical properties.
Optical isomers differ from each other in their interactions

with plane-polarized light.
37
The structural
relationship between
two optical isomers is
analogous to the
relationship between
your left and right
hands.
38

The cis and trans isomers of
dichlorobis(ethylenediamine)cobalt(III) ion and the mirror
image of each.
The cis isomer and its mirror image are optical isomers.
39
Optical isomers are described as chiral.
Chiral molecules are nonsuperimposable.
Isomers that are superimposable with their mirror images are

said to be achiral.
40

Chiral molecules are optically active because of their ability to
rotate polarized light as it passes through them.
Unlike ordinary light, which vibrates in all directions, plane-

polarized light vibrates only in a single plane.
We use a polarimeter to measure the rotation of polarized

light by optical isomers.
41

If the plane of polarization is rotated to the right, the isomer
is dextrorotatory and is labeled d.
If the rotation is to the left, the isomer is levorotatory and is

labeled l.
The d and l isomers of a chiral substance, called enantiomers,

always rotate the plane of polarization by the same amount,
but in opposite directions.
42

In an equimolar mixture of two enantiomers, called a racemic
mixture, the net rotation is zero.
43
22.3 Bonding in Coordination Compounds: Crystal
Field Theory
Topics
Crystal Field Splitting in Octahedral Complexes
Color
Magnetic Properties
Tetrahedral and Square Planar Complexes
44
Field Theory
Crystal field theory accounts for the color and magnetic
properties of many coordination compounds.
In a complex ion, two types of electrostatic interaction come

into play.
1. the attraction between the positive metal ion and the
negatively charged ligand
2. the electrostatic repulsion between the lone pairs on the
ligands and the electrons in the d orbitals of the metals
45
Field Theory
The d orbitals have different orientations but the same
energy, in the absence of an external disturbance.
In an octahedral complex, a central metal atom is surrounded

by six lone pairs of electrons, so all five d orbitals experience
electrostatic repulsion.
The magnitude of this repulsion depends on the orientation

of the d orbital that is involved.
.
46
Field Theory
The lobes of the dx2 ‒ y2 orbital point toward the corners of the
octahedron along the x and y axes, where the lone-pair
electrons are positioned.
An electron residing in this orbital would experience a greater

repulsion from the ligands than an electron would in the dxy,
dyz, or dxz orbitals.
The energy of the dx2 ‒ y2 orbital is increased relative to the dxy,

dyz, or dxz orbitals.
47
Field Theory
The dz2 orbital’s energy is also greater, because its lobes are
pointed at the ligands along the z axis.
48
Field Theory
The five d orbitals in an octahedral complex are split between
two sets of energy levels.
49
Field Theory
The crystal field splitting (Δ) is the energy difference between
two sets of d orbitals in a metal atom when ligands are
present.
The magnitude of Δ depends on the metal and the nature of

the ligands.
It has a direct effect on the color and magnetic properties of

complex ions.
50
Field Theory
Color
White light is a combination of all colors.
A substance appears black if it absorbs all the visible light that

strikes it.
An object appears green if it absorbs all light but reflects the

green component.
51
Field Theory
Color
An object also looks green if it reflects all colors except red,
the complementary color of green.
The best way to measure

crystal field splitting is to
use spectroscopy to
determine the wavelength
at which light is absorbed.
52
Field Theory
Color
The [Ti(H2O)6]3+ ion

absorbs light in the
visible region of the
spectrum with a
maximum absorption
at 498 nm.
53
Field Theory
Color
To calculate the crystal field splitting energy, recall
Therefore,
This is the energy required to excite one [Ti(H2O)6]3+ ion.
54
Field Theory
Color
To express this energy difference in units of kJ/mol, we write
55
Field Theory
Color
Chemists have calculated the crystal field splitting for each
ligand and established the following spectrochemical series,
These ligands are arranged in the order of increasing Δ.
CO and CN‒ are called strong-field ligands, because they

cause a large splitting of the d orbital energy levels.
The halide ions and hydroxide ion are weak-field ligands,

because they split the d orbitals to a lesser extent.
56
Field Theory
Magnetic Properties
The magnitude of the crystal field splitting also determines
the magnetic properties of a complex ion.
The configuration
of Fe3+ is [Ar]3d5,
and there are two
possible ways to
distribute the five
d electrons among
the d orbitals.
57
Field Theory
Magnetic Properties
The actual arrangement of the electrons is determined by the
amount of stability gained by having maximum parallel spins
versus the investment in energy required to promote
electrons to higher d orbitals.
Because F‒ is a weak-field ligand, the five d electrons enter

five separate d orbitals with parallel spins to create a high-
spin complex.
58
Field Theory
Magnetic Properties
The CN‒ is a strong-field ligand, so it is energetically preferable
for all five electrons to be in the lower orbitals, thus forming a
low-spin complex.
High-spin complexes are more paramagnetic than low-spin

complexes
59
Field Theory
Magnetic Properties
A distinction
between low- and
high-spin complexes
can be made only if
the metal ion
contains > 3 and < 8
d electrons
60
SAMPLE PROBLEM 22.4
Predict the number of unpaired spins in the [Cr(en)3]2+ ion.
61
SAMPLE PROBLEM 22.4
Setup
The electron configuration of Cr2+ is [Ar]3d4; and en is a
strong-field ligand.
Solution
Because en is a strong-field ligand, we expect [Cr(en)3]2+ to be
a low-spin complex.
All four electrons will be placed in the lower-energy d orbitals

and there will be a total of two unpaired spins.
62
Field Theory
The splitting pattern for a tetrahedral ion is the reverse of that
for octahedral complexes.
Most tetrahedral complexes are high-spin complexes.
63
Field Theory
The splitting pattern for square-planar complexes is the most
complicated.
64
Topics
Reactions of Coordination Compounds
65

Complex ions undergo ligand exchange (or substitution)
reactions in solution.
It is useful to distinguish between the stability of a complex

ion and its tendency to react, which we call kinetic lability.
Stability in this context is a thermodynamic property, which is

measured in terms of the species’ formation constant Kf .
66

For example, the complex ion tetracyanonickelate(II) is stable
because it has a large formation constant (Kf = 1 × 1030):
Complexes like the tetracyanonickelate(II) ion are termed

labile complexes because they undergo rapid ligand exchange
reactions.
Thus, a thermodynamically stable species (i.e., one that has a

large formation constant) is not necessarily unreactive.
67

A complex that is thermodynamically unstable in acidic
solution is [Co(NH3)6]3+.
This is an example of an inert complex—a complex ion that

undergoes very slow exchange reactions.
It shows that a thermodynamically unstable species is not

necessarily chemically reactive.
68

The rate of reaction is determined by the energy of activation.
Most complex ions containing Co3+, Cr3+, and Pt2+ are

kinetically inert.
69
Topics
Applications of Coordination Compounds
70

Metallurgy
Examples of the use of coordination compounds in

metallurgical processes:
• extraction of silver and gold by the formation of cyanide

complexes
• purification of nickel
71

Chelation Therapy
Chelation therapy is used in the treatment of lead poisoning.
Arsenic and mercury can also be removed using chelating

agents.
72

Chemotherapy
Several platinum-containing coordination compounds,
including cisplatin [Pt(NH3)2Cl2] and carboplatin
[Pt(NH3)2(OCO)2C4H6], can effectively inhibit the growth of
cancerous cells.
The mechanism for the action of cisplatin is the chelation of

DNA. This causes a bend in the double-stranded structure
which inhibits replication. The damaged cell is then destroyed
by the body’s immune system.
73

Chemical Analysis
Dimethylglyoxime forms an insoluble brick-red solid with Ni2+
and an insoluble bright-yellow solid with Pd2+.
These characteristic colors are used in qualitative analysis to

identify nickel and palladium.
The quantities of ions present can be determined by

gravimetric analysis.
74

Detergents
The cleansing action of soap in hard water is hampered by the
reaction of the Ca2+ ions in the water with the soap molecules
to form insoluble salts or curds.
The detergent industry used tripolyphosphate ion as a

chelating agent to form stable complexes with Ca2+ ions .
However, wastewater containing phosphates discharged into

rivers and lakes causes algae to grow, resulting in oxygen
depletion.
75

Sequestrants
EDTA is used as a food additive to sequester metal ions.
EDTA sequesters Cu, Fe, and Ni ions that would otherwise

catalyze the oxidation reactions that cause food to spoil.
EDTA is a common preservative in a wide variety of consumer

products.
76

Coordination Chemistry

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Chemistry

Properties of Transition Metals

A coordinate covalent bond is a covalent bond in which one of

A coordination compound often consists of a complex ion and

Properties of Transition Metals

Most of the metals in coordination compounds are transition

Properties of Transition Metals

Properties of Transition Metals

Incompletely filled d subshells give rise to several properties:

Properties of Transition Metals

Properties of Transition Metals

Properties of Transition Metals

All these metals can exhibit

The highest oxidation state for

To be a ligand, a molecule or ion must have at least one

The coordination number of Cu2+ in [Cu(NH3)4]2+ is 4.

The most common coordination numbers are 4 and 6.

In the complex ion [PtCl6]2‒, each chloride ion ligand has an

a) The complex ion is [Ru(NH3)5(H2O)]2+. Each ligand is

b) The complex ion is [Cr(NH3)6]3+. Each ligand is neutral.

c) Fe(CO)5 does not contain a complex ion. The ligands are

Nomenclature of Coordination Compounds

1. The cation is named before the anion. The rule holds

2. Within a complex ion, the ligands are named first, in

Nomenclature of Coordination Compounds

4. When two or more of the same ligand are present, use

Nomenclature of Coordination Compounds

6. If the complex is an anion, its name ends in –ate.

Nomenclature of Coordination Compounds

Nomenclature of Coordination Compounds

b) The cation is K+, and the anion is a complex ion with a

b) K3[Fe(CN)6] Potassium hexacyanoferrate(III)

(a) pentaamminechlorocobalt(III) chloride

(b) dichlorobis(ethylenediamine)platinum(IV) nitrate

b) There are two bidentate ethylenediamines and two Cl‒

a) [Co(NH3)5Cl]Cl2 (pentaamminechlorocobalt(III) chloride)

Structure of Coordination Compounds

Structure of Coordination Compounds

Stereoisomers have distinctly different physical and chemical

Coordination compounds may exhibit two types of

Structure of Coordination Compounds

Geometric isomers come in pairs: cis and trans.

Cis means that two particular atoms are adjacent to each

Trans means that the atoms are on opposite sides in the

Structure of Coordination Compounds

Structure of Coordination Compounds

Structure of Coordination Compounds

Optical isomers also come in pairs.

The optical isomers of a compound have identical physical

Optical isomers differ from each other in their interactions

Structure of Coordination Compounds

Structure of Coordination Compounds

Structure of Coordination Compounds

Optical isomers are described as chiral.

Chiral molecules are nonsuperimposable.

Isomers that are superimposable with their mirror images are

Structure of Coordination Compounds

Unlike ordinary light, which vibrates in all directions, plane-

We use a polarimeter to measure the rotation of polarized

Structure of Coordination Compounds

If the rotation is to the left, the isomer is levorotatory and is

The d and l isomers of a chiral substance, called enantiomers,

Structure of Coordination Compounds

In a complex ion, two types of electrostatic interaction come