Chapter 6 An Introduction to Coordination Compounds

[Ar]

[Kr]

[Xe]

21

22

23

24

25

26

27

28

Sc

Ti

Cr

Mn

Fe

Co

Ni

3d14s2

3d24s2

3d34s2

3d54s1

3d54s2

3d64s2

3d74s2

3d84s2

39

40

41

42

43

44

45

45

Zr

Nb

Mo

Tc

Ru

Rh

Pd

4d15s2

4d25s2

4d45s1

4d55s1

4d55s2

4d75s1

4d85s1

4d10

57

72

73

74

75

76

77

78

La

Hf

Ta

Re

Os

Ir

Pt

5d16s2

4f145d26s2

4f145d36s2

4f145d46s2

4f145d56s2

4f145d66s2

4f145d76s2

4f145d96s1

To write the electronic structure for Co2+:

The Nobel Prize in Chemistry 1913

Alfred Werner (University of Zurich, Switzerland)
"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
especially in inorganic chemistry
Prior to Werner's work, it was not known how the atoms in a
molecule of the chemical formula [Pt(NH3)2Cl2] were connected.
The theories at the time predicted such molecules to be connected
as linear chains: [Pt-NH3-NH3-Cl]Cl or Cl-NH3-Pt-NH3-Cl

To write the electronic structure for V3+:

Co

[Ar] 3d74s2

[Ar] 3d34s2

Co2+

[Ar] 3d7

V3+

[Ar] 3d2

Compound

Chapter 8

Historic name

CoCl3 6 NH3

Yellow

Luteo-complex

CoCl3 5 NH3

purple

Purpureo-complex

CoCl3 4 NH3

Green

Praseo-complex

CoCl3 4 NH3

Violet

Violeo-complex

Werner studied the conductivities of solutions. Other factors being

equal, the conductivity of an aqueous solution of an ionic salt is
proportional to the number of ions produced when the salt is dissolved.

Chapter 8

Based on the postulations, Werner formulated the compounds

[Pt(NH3)6]Cl4
[Pt(NH3)5Cl]Cl3
[Pt(NH3)4Cl2]Cl2
[Pt(NH3)3Cl3]Cl
[Pt(NH3)2Cl4]
K[Pt(NH3)Cl5]
K2[PtCl6]

Werner studied the following series:

Pt(NH3)6Cl4
has relatively high conductivity (more ions)
Pt(NH3)5Cl4
has decreasing conductivity
Pt(NH3)4Cl4
has decreasing conductivity
Pt(NH3)3Cl4
has decreasing conductivity
Pt(NH3)2Cl4
has zero conductivity
KPt(NH3)Cl5
has increasing conductivity
K2PtCl6
has increasing conductivity

has relatively high conductivity (more ions)

has decreasing conductivity
has decreasing conductivity
has decreasing conductivity
has zero conductivity
has increasing conductivity
has increasing conductivity
(4-n)+

[Pt(NH3)6-nCln]

These experiments led Werner to postulate the presence of 2 different

types of bonding in inorganic coordination compounds:
1. Primary valences, fixed in number by charge balance; these
were ionic (i.e. to ions only) and non-directional.
2. Secondary valences, determined by the nature of the central
metal atom (usually 4 or 6); non-ionic, directional.
Chapter 8

Color

1-

(Cl )4-n

Coordination chemistry
Transition metals can form a variety of coordination compounds
3

Chapter 8

Compound

Color

Historic name

CoCl3 6 NH3

Yellow

Luteo-complex

Some important concepts and definitions

Complex: A central metal ion (atom) bonded via coordinate bonds
to one or more molecules or ions called ligands
Complex ion complex with net charge
coordination number number of coordinate bonds between metal
ion and the ligand or ligands
Coordination compound: (1) neutral substance made up of complex
ion and another ion of opposite charge.
(2) neutral complex
Ligand: contains at least one nonbonding pair of electrons
Some important aspects of transition metal ions
(1) The valence electrons are in d orbitals
(2) The d orbitals do not have large radial extension. They are therefore
mostly nonbonding in complexes of transition metal ions

Chapter 8

Molecular orbital diagram for an octahedral complexes

MO description of Metal-Ligand interactions

t1u

Antibonding

Chapter 8

t1u

L ligand

18-electron complexes d6 complexes

a1g

a1g

eg
eg + t2g

t2g

L ligand

t1u

a1g + t1u + eg
eg

a1g

L ligand

L
L
Chapter 8

LGOs

Bonding

M
L

L
Chapter 8

Valence bond description

a ligand-to-metal dative bond
metal center

L ligand

metal empty
hybridized orbital

ligand orbital
accomodating a lone pair of electrons

Chapter 8

Chapter 8

10

Monodentate, bidentate, tridentate, polydentate ligands

Ligands

H
C

H3C

Ligands bond to a metal through 1, 2, 3, atoms

Chapter 8

11

Chapter 8

CH3

H
C

H3C

CH3

12

Chapter 8

13

Chapter 8

14

The Concept of Coordination Numbers

The concept of coordination numbers was an important result of Werner's
research. It clearly established the two most important aspects that are
required to discuss chemical structure and change:
oxidation state and coordination number.
The concept of oxidation state implies that we have knowledge who
loses electrons and who gains electrons in a compound. This cannot be
done unambiguously unless generally accepted rules are applied.
The concept of coordination number is a geometric concept and simply
represents the number of next neighbors. It is important to realize that the
concept of coordination numbers does not imply any specific type of
bonding. Dative bonds, hydrogen bridge bonding, single, double or triple
bonds indeed any type of bond (including those found in solids) is
permissible. It is this generality of the concept that makes the concept so
valuable.
Chapter 8

15

Chapter 8

16

Coordination number 2
i

Pr

Coordination number 1

Stable compounds
with coordination
number 2 are
restricted to the
copper group (Cu,
Ag, Au) and to
mercury.

Pr

Complexes with coordination

number 1 were erroneously
claimed for copper and silver,
but a genuine metal complex
with CN= 1 (M = Indium) was
recently reported by P. Power
(S. T. Haubrich, P. Power,
JACS 1998, 120, 2202-2203)

Pr

In
i

Pr

Pr
i

Pr

Also rare, typical of d10, linear structures,

no possible isomers
Very rare, bulky ligands, linear structures, no possible isomers
Chapter 8

17

Coordination number 3

Chapter 8

18

Chapter 8

20

Coordination number 4
Tetrahedral geometry

Also typical of d10, trigonal planar structures (rarely T-shaped), no possible isomers
Chapter 8

19

Coordination number 4

Coordination number 5

Square-planar geometry

Square-pyramidal (SP)
Trigonal bipyramidal (TBP)

Chapter 8

21

Very similar energies, they may easily interconvert in solution (fluxionality)

Chapter 8

22

Coordination number 6
Octahedral (most common)
Trigonal prismatic (TP) (less common)

A Berry pseudorotation

Chapter 8

23

Chapter 8

24

Coordination number 7

Coordination number 8

(very uncommon)

Dodecahedron

Capped octahedral

Cube

Square antiprism

Point group?

Capped
Pentagonal bipyramidal
trigonal prismatic

NbF72Inorg Chem 1969, 8, p2680

Chapter 8

[FeL(NCS)2] +(ClO4)JACS, 1967, 89, 720

[Mo(CN)8]3-

25

Coordination number 9
Tricapped trigonal prism (TTP)

[Zr(ox)4]4-

Chapter 8

26

Isomerism

[ReH9]2Eu(H2O)9]3+
Coordination number 10-12

[Ce(NO3)5]2Bicapped square
antiprism

Cis and trans

isomers

icosahedron
[Ce(NO3)6]3Chapter 8

27

Chapter 8

Mirror images

28

Structural isomers

Linkage isomers
Linkage isomers are two or more coordination compounds in which the
donor atom of at least one of the ligands is different (i.e., the connectivity
between atoms is different)

Two types of structural isomers are linkage isomerism and

coordination-sphere isomers.
Coordination sphere isomers: ratio of ligand:metal same, but
ligands are attached to metal ions in different numbers

[Cr(H2O)6]Cl3, violet
[CrCl(H2O)5]Cl2.H2O, blue-green
[CrCl2(H2O)4]Cl.2H2O, dark green
[CrCl3(H2O)3].3H2O, yellow green
3+

OH2
H2 O

Cr

[CoIII(NH3)5Br]SO4
[CoIII(NH3)5SO4] Br

2+

Cl
OH2

H2O

OH2

3Cl-

H2 O

H2 O

Cr

H2 O

violet

OH2
OH2

H2 O

green
Chapter 8

2Cl-

Similarly, SCNcan coordinate

through S or N.

Cl
H2 O

Cr

H2 O

OH2

Cl-

OH2

trans-[RuCl(py)4(NO)]+

Cl

Phys. Chem. Chem. Phys.,

2007, 9, 3717 - 3724

green
29

Stereoisomers

Chapter 8

30

Octahedral complexes

Stereoisomers are isomeric molecules whose atomic connectivity is the

same but whose atomic arrangement in space is different.
Geometric isomers
Geometric isomers are stereoisomers where the two forms are not mirror
images of each other.

fac (facial)

mer (meridional)

cis

trans

Square planar complexes

Chapter 8

31

Chapter 8

32

Geometrical isomers in
Trigonal bipyramidal complexes
Pentagonal bipyramidal complexes
and etc others

apical

basal

Chapter 8

33

Chapter 8

34

Optical isomers (are also called enantiomers )

Non-identical mirror images with the same geometric arrangement of ligands.
A set of two (mirror image) isomers are called enantiomers.

Chapter 8

35

Enantiomers differ only in optical properties rotate plane-polarized light in

opposite directions.

Chapter 8

36

Stereoisomerism
Pasteur was the first to separate racemic ammonium tartarate
(NaNH4C4H9O6) by crystallizing the solution and physically picking out
the right-handed crystals from the mixture using a microscope.
Optically pure tartarate can be used to separate a racemic mixture of
[Co(en)3]Cl3: if d-tartarate is used, d-[Co(en)3]Cl3 precipitates leaving l[Co(en)3]Cl3 in solution.

Stereoisomerism

Enantiomers are capable of rotating the plane of polarized light.

Hence, they are called optical isomers.
When horizontally polarized light enters an optically active solution, the
plane of polarity has changed as the light emerges from the solution.
The mirror image of an enantiomer will rotate the plane of polarized
light by the same amount in the opposite direction.

Tetrahedral complexes
similar to compounds having an sp3-carbon center

Dextrorotatory solutions rotate the plane of polarized light to the right.

This isomer is called the d-isomer.
Levorotatory solutions rotate the plane of polarized light to the left.
This isomer is called the l-isomer.
Chiral molecules are optically active because of their effect on light.
Racemic mixtures contain equal amounts of l- and d-isomers. They
have no overall effect on the plane of polarized light.

Octahedral complexes
those with chelating ligands

Chapter 8

37

Chapter 8

38

Chapter 8

39

Chapter 8

40

10

L
L

L
L

Two absolute
configurations:

L
L

L
L

1
4

4
6

configuration (lamda)
greek stands for
laevo or left

4
2

dextro or right

(delta)
configuration
greek stands for

2
6

Chapter 8

41

Chapter 8

42

11