COORDINATION

COMPOUNDS
COORDINATION COMPOUNDS
By now, you have learnt about

(i) Transition elements

(ii) The general characteristics of transition elements
(iii) Electronic configurations of the first-row elements
(iv) Variable oxidation states of the transition elements

In section B of this module, you are going to learn about compounds formed by the transition
elements – coordination compounds.

(i) Definitions and terminology

(ii) Nomenclature
(iii) Isomerism

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Coordination compounds – Definitions
and terminology
• Coordination complex – a compound that results from a coordinate bond
formation between a ligand and a transition metal ion

• Ligands possess lone pair of electrons.

• Transition elements possess vacant orbitals.

• A coordinate bond involves the ligand donating an electron pair to the central ion.

• The atom in the ligand which can donate an electron pair is called the donor
atom/coordinating atom.
Coordination compounds (CCs)–
Definitions and terminology
• A coordination compound contains a complex ion

• A complex ion is an electrically charged ion which consists of a central metal atom
ion surrounded by a group of ions or neutral molecules (ligands)

• For example in the CC, [Ni(NH3)6]Cl2 - Ni2+ is the central ion and NH3 is the ligand
and [Ni(NH3)6]2+

• Identify the complex ion, central ion and the ligands in the CC, Na3[Fe(CN)6]
• For example [Cu(NH3)4]SO4 contains the complex ion [Cu(NH3)4]2+
• What is the complex ion in K[Ag(CN)2]?
• The atom in the ligand which can donate an electron pair is called the
donor atom/coordinating atom
Coordination sphere
• The central atom together with molecules or ions coordinated to it
constitute the coordination sphere

• When writing the formula of complex ions the central ion together
with its coordination sphere is written inside square brackets
Coordination number
• The total number of ligands attached to a central ion is called the coordination
number

• What is the coordination number of Ag+ in [Ag(CN)2]-

Cu2+ in [Cu(NH3)4]2+
Co3+ in [CoCl (NH ) ]
Charge on the complex ion

The charge carried by a complex ion is the sum of the charges on the central atom and
the ligands coordinated to it

[Cu(NH3)4]2+

Has a net charge of +2

[Fe(CN)6]4-

Has a net charge of -4

Types of ligands
A ligand can contain one or more donor atoms. Ligands are classified as
follows:
1. Unidentate or monodentate – donate
only one pair of electrons. Coordinate
via one donor atom, e.g. CN-, H2O, Cl-,
Br-, NH3, OH-, NO2-, CO

2. Bidentate - coordinate via two donor atoms

3. Polydentate – coordinate via more than two

donor atoms eg tridentate, tetradenate,
pentadentate, hexadentate
Anionic Ligands Names Neutral Ligands Names
Br- bromo NH3 ammine
F- fluoro H2 O aqua
O2- oxo NO Nitrosyl
OH- Hydroxo CO Carbonyl
CN- cyano O2 dioxygen
C2O42- oxalato N2 dinitrogen
CO32- carbonato C5 H5 N pyridine
CH3COO- acetato H2NCH2CH2NH2 Ethylenediamine
(en)
SO42- sulphate Cationic ligands Names

NO3- Nitrato NO+ Nitrosonium

Nitrito-N NO2- NH2NH3+ Hydrazinium

Nitrito-O ONO- NO2+ Nitronium
Calculating oxidation number
What is the oxidation number of the metal ion in each of the following
complexes
• [Co(NH3)6]Cl3
• [CoSO4(NH3)4]NO3
• [Cd(SCN)4]2+
• [Cr(en)3]Cl3
Chelating ligands and chelates

A ligand is termed a chelating ligand if it coordinates to a metal center

forming a ring structure . The resulting complex is called a chelate
 H 3N Ag NH 3
Cl 2- N H3
H 3N

Pt
Cu
Cl Cl

Cl Cl

Cl 2-

[Ag(NH3)2]+ [CuCl4] [Pt(NH3)2Cl2]

H2O N H3 3+ 2+
H2O
H 2O NH 3
NH NH 3
H 2O 3 NH 3

Cu Co
Cu

N H3 N H3
H2O H2O N H3 N H3
N H3
H2O H2O

[Cu(H2O)6]2+ [Co(NH 3)6] 3 +

(a) [Cd(SCN)4]2-
 Identify the ligand, central metal ion and counter ion
SCN-, Cd2+, no counterion

 Write down the formula for the complex ion Calculating the oxidation state / number of the metal ion
[Cd(SCN)4]2-
Cd + 4(-1) = -2
 Is the complex ion cationic or anionic? Cd = +2
anionic = Cd2+

 What is the charge on the complex ion? 2-

-2
 Is the ligand bidentate, monodentate or polydentate
Monodentate

 What is the coordination number of the central metal ion

4
 A coordinate bond is formed between which atoms?
Cd and S
 (b) [Cr(en)3]Cl3
 Identify the ligand, central metal ion and counter ion
ethylenediamine (en), Cr3+, Cl-

 Write down the formula for the complex ion

[Cr(en)3]3+ Calculating the oxidation state / number of the metal ion

 Is the complex ion cationic or anionic? Cr + 3(0)+3(-1) = 0

Cation Cr = +3
= Cr3+
 What is the charge on the complex ion?
+3
 Is the ligand bidentate, monodentate or polydentate
bidentate

 What is the coordination number of the central metal ion

6

 A coordinate bond is formed between which atoms?

Cr and N
(c) [PtCl2 (en)2]Cl2
 Identify the ligand, central metal ion and counter ion
ethylenediamine (en) and Cl-, Pt4+, Cl-

 Write down the formula for the complex ion

[PtCl2 (en)2]2+
Calculating the oxidation state / number of the metal ion

 Is the complex ion cationic or anionic? Pt + 2(-1)+2(0)+2(-1) = 0

Cation Pt = +4
= Pt4+
 What is the charge on the complex ion?
+2
 Is the ligand bidentate, monodentate or polydentate
en = bidentate, Cl = monodentate

 What is the coordination number of the central metal ion

6

 A coordinate bond is formed between which atoms?

Pt and N, and Pt and Cl
(d) Na3[FeCl(CN)5],
 Identify the ligand, central metal ion and counter ion
CN- and Cl-, Fe3+, Na+
Calculating the oxidation state / number of the metal ion
 Write down the formula for the complex ion
[FeCl(CN)5]3- Fe + 1(-1)+5(-1)+3(+1) = 0
Fe = +3
 = Fe3+
Is the complex ion cationic or anionic?
anionic

 What is the charge on the complex ion?

-3

 Is the ligand bidentate, monodentate or polydentate

Cl- and CN- = monodentate

 What is the coordination number of the central metal ion

6

 A coordinate bond is formed between which atoms?

Fe and Cl-, and Fe and C for CN-
(e) (NH4)2[Ni(C2O4)2(H2O)2] Oxalato
 Identify the ligand (s), central metal ion and counter ion
C2O42-, Ni2+, NH4+

Calculating the oxidation state / number of the metal ion

 Write down the formula for the complex ion
[Ni(C2O4)2(H2O)2]2-
Ni + 2(-2)+2(0)+2(+1) = 0
Ni = +2
 Is the complex ion cationic or anionic? = Ni2+
anionic

 What is the charge on the complex ion?

-2

 Is the ligand bidentate, monodentate or polydentate

H2O = monodentate, C2O42- = bidentate

 What is the coordination number of the central metal ion

6
 A coordinate bond is formed between which atoms?
Ni and O
Nomenclature of coordination compounds

You will be required to write the IUPAC formula of a coordination compound,

given the name

For example: Write down the formula of the following compound

Name: pentaamminechloroplatinum(IV) bromide

Answer: [PtCl (NH3)5]Br3

The names and formula of coordination compounds are written following the rules developed by the international of pure
and applied chemistry (IUPAC)
How to write the formula of coordination compounds
1. The central atom is written first, anionic ligands are listed next followed by neutral ligands

eg, [PtCl (NH3)5]Br3

2. If there are more than one anionic ligands, they are listed in alphabetical order according to the
first symbol of their formula

Na3[FeCl(CN)5],

3. A similar procedure is followed if there are more than two neutral ligands

4. Polyatomic ligands are written in parenthesis (in brackets) eg NH3, H2O,

eg the complex triamminebromochloroiodocobalt(III) is written as [CoBrClI(NH3)3] and not as

[Co(NH3)3BrClI]
How to write the formula of coordination compounds

5. Complicated ligands are listed in their commonly accepted abbreviations in

parenthesis

Eg [PtCl2 (en)2]2+

Ethylenediamine is written as ‘en’

6. The whole formula of a coordination sphere is enclosed in a square bracket

[PtCl2 (en)2]2+
 How to write the formula of coordination compound
rules for naming metal ion in cationic and anionic complexes are different

potassium hexafluorocobaltate(III) Anionic complex

For cationic complex, the an ate is added to the

name of the metal, except for the metal ions
listed below

sodium chloropentacyanoferrate(III)

pentaamminechloroplatinum(IV) bromide Cationic complex

The name of the metal remains the same

Give the IUPAC formula of sodium
chloropentacyanoferrate(III)
Solution
Space separates counterion coordination sphere
sodium chloropentacyanoferrate(III)
Na Cl- 5 CN- Fe
Oxidation number

Coordination sphere
counterion

Naming the coordination sphere

The central atom is written first, anionic ligands are listed next followed by neutral ligands

[FeCl(CN)5]X
Calculating the charge on the complex ion If the charge on the complex ion is -3, then 3 Na+ are
needed to balance the charge, therefore formula of the compound is
+3+1(-1)+5(-1) = X
X = -3 [FeCl(CN)5]3- Na3[FeCl(CN)5]
Give the IUPAC formula of pentaamminechloroplatinum(IV)
bromide
Oxidation number
Solution Space separates the coordination sphere from the counterion

Name: pentaamminechloroplatinum(IV) bromide

5 NH3 Cl- Pt Br

Coordination sphere counterion

[PtCl (NH3)5]x? The central atom is written first, anionic ligands are listed next followed by neutral
ligands
Calculating the charge on the complex ion

The charge on the complex ion is the sum of charges of the ligand and the metal ion

X = +4 + 1(-1) + 5 (0) [PtCl (NH3)5]Br3

X = +3 [PtCl (NH3)5] 3+
answer
Na2[NiCl4]

Answer: sodium tetrachloronickelate(II)

Solution: The complex ion is the anion so we have to add the suffix –ate in the name
of the metal.
Write down the IUPAC formula of the following compounds

1. hexaammineiron(III) nitrate

2. ammonium tetrachlorocuprate(II)

3. potassium hexafluorocobaltate(III)
Answers

1. [Fe(NH3)6](NO3)3
2. (NH4)2[CuCl4]
3. K3[CoF6]
Give the molecular formulas of the following coordination compounds?

1. hexaammineiron(III) nitrate

2. ammonium tetrachlorocuprate(II)
3. sodium chloropentacyanoferrate(III)
4. potassium hexafluorocobaltate(III)
Nomenclature of coordination compound according to IUPAC

You will be required to write the name of a compound when given the
formula

1. Order of naming ions – The cation is named first and then the anion.

I. [Ag(NH3)2]Cl Diamminesilver(I) chloride

II. [Co(CO3)(NH3)4]Cl Pentaamminecarbonatocobalt(III) chloride
III. K4[Fe(CN)6] Potassium hexacyanoferrate(II)
Nomenclature of coordination compound according to IUPAC
1. Order of naming ions – in ionic coordination complexes, the cation is named first and then the
anion.

I. [Ag(NH3)2]Cl Diamminesilver(I) chloride

II. [Co(CO3)(NH3)4]Cl Pentaamminecarbonatocobalt(III) chloride
III. K4[Fe(CN)6] Potassium hexacyanoferrate(II)

Neutral ions are given a one word name.

[PtCl4(NH3)2] diamminetetrachloroplatinum(IV)
[Co(NO2)3(NH3)3] Triamminetrinitrito –Ncobalt(II)

2. Naming the coordination sphere – The ligands are named first and then the central metal ion

3. Names of the ligands – The names of negative ligands end in o and of positive ligands end in um

4. Order of naming ligands –ligands are named in alphabetical order irrespective of their being neutral,
cationic or anionic eg [PtCl(NO2)(NH3)4] - the ligand are named in order ammine, chloro and nitrito- N
Anionic Ligands Names Neutral Ligands Names
Br- bromo NH3 ammine
F- fluoro H2 O aqua
O2- oxo NO Nitrosyl
OH- Hydroxo CO Carbonyl
CN- cyano O2 dioxygen
C2O42- oxalato N2 dinitrogen
CO32- carbonato C5 H5 N pyridine
CH3COO- acetato H2NCH2CH2NH2 ethylenediamine
SO42- sulphate Cationic ligands Names

NO3- Nitrato NO+ Nitrosonium

Nitrito-N NO2- NH2NH3+ Hydrazinium

Nitrito-O ONO- NO2+ Nitronium
5. Prefixes to indicate number of ligands - prefixes are used to designate the number of each
type of ligand in the complex ion, e.g. di-, tri- and tetra-.

Ligands with complex names such as ethylenediamine or triphenylphosphine, the prefixes

bis-, tris-, tetrakis-, pentakis-, are used instead

6. Ending of names – When the complex is anionic, the name of the central ion ends with
ate. For cationic and neutral complexes, the name is given without any characteristic ending
eg K[PtCl5(NH3)] which contains the complex ion [PtCl5(NH3)]- is named potassium
amminepentachloroplatinum(IV)

[Fe(H2O)6]SO4 contains the cationic complex [Fe(H2O)6]2+ is named hexaaqua iron(II) sulphate

7. Oxidation state of the central ion – the oxidation state is designated by a Roman numeral
at the end of the name of a complex
[PtCl(NO2)(NH3)4]SO4 is named tetramminechloronitrito-Nplatinum(IV) sulphate

8. Bridging groups – ligands which act as bridges between two metal atoms, the greek
symbol µ is used.

9. Points of attachment – for ligands that coordinate through one or the other atom,
NO2- (coordinating via N) is called nitrito –N
ONO- (coordinating via O) is called nitrito-O
SCN- - thiocyanato S
NCS- - thiocyanato N
10. Naming of geometrical isomers – geometrical isomers are general named
by the use of cis to designate adjacent positions and trans to designate
opposite positions

11. Abbreviations for complicated molecules – for molecule with long

complicated names, abbreviations are used eg
Ethylenediamine – en
Pyridine – py
Acetylacetanato - acac
Name of Metals in Anionic Complexes
Name of Metal Name in an Anionic
Complex

Iron Ferrate

Copper Cuprate

Lead Plumbate

Silver Argenate

Gold Aurate

Tin Stannate
Class exercise

1. [Cr(NH3)3(H2O)3]Cl3
Solution: The complex ion is a cation.
• The ammine ligands are named before the aqua ligands according to alphabetical order.

• Since there are three chlorides binding with the complex ion, the charge on the complex
ion must be +3 ( since the compound is electrically neutral).

• From the charge on the complex ion and the charge on the ligands - calculate the
oxidation number of the metal. In this example, all the ligands are neutral molecules.
Therefore, the oxidation number of chromium must be same as the charge of the complex
ion, +3.
• Answer: triamminetriaquachromium(III) chloride
2. [PtCl (NH3)5]Br3
2. [PtCl (NH3)5]Br3

• Answer: pentaamminechloroplatinum(IV) bromide

• Solution: The complex ion is a cation, the counter anion is the 3

bromides.

The charge of the complex ion must be +3 since it bonds with 3 bromides.

The NH3 are neutral molecules while the chloride carries - 1 charge.
Therefore, the oxidation number of platinum must be +4.
• 3. [PtCl2 (en)2]Cl2
• 3. [PtCl2 (en)2]Cl2

Answer: dichlorobis(ethylenediamine)platinum(IV) chloride

• Solution: ethylenediamine is a bidentate ligand, the bis- prefix is used
instead of di-
4. K4[Fe(CN)6]
4. K4[Fe(CN)6]

• Answer: potassium hexacyanoferrate(II)

• Solution: potassium is the cation and the complex ion is the anion

Since there are 4 K+ binding with a complex ion, the charge on the complex
ion must be - 4.

Since each ligand carries –1 charge, the oxidation number of Fe must be

+2.

The common name of this compound is potassium ferrocyanide.

5. Na2[NiCl4]
5. Na2[NiCl4]
• Answer: sodium tetrachloronickelate(II)
Solution: The complex ion is the anion so we have to add the suffix –ate in the
name of the metal.
9. (NH4)2[Ni(C2O4)2(H2O)2]
9. (NH4)2[Ni(C2O4)2(H2O)2]

Answer: ammonium diaquabis(oxalato)nickelate(II)

Solution: The oxalate ion is a bidentate ligand.
9. (NH4)2[Ni(C2O4)2(H2O)2]

Answer: ammonium diaquabis(oxalato)nickelate(II)

Solution: The oxalate ion is a bidentate ligand.
10. [Co(en)3]Cl3
10. [Co(en)3]Cl3

Tris(ethylenediamine)cobalt(III) chloride
Give the names for the following compounds

[Co(SO4)(NH3)5]+

[Fe(OH)(H2O)5]2+

[Ag(CN)2]-
Give the names for the following compounds

[Co(SO4)(NH3)5]+

pentaamminesulfatocobalt(III) ion

[Fe(OH)(H2O)5]2+

pentaaquahydroxoiron(III) ion

[Ag(CN)2]-

dicyanoargentate(I)anion
Chelating ligands

When a bidentate or a polydentate

ligand is attached via two or
more donor atoms to the same
central metal ion

The ligand is called a chelating

ligand
Bridging ligands
- A bridging ligand is a ligand that connects two or more atoms, usually metal
ions.
Effective Atomic Number (EAN)

Transition elements form coordination compounds because they have vacant d

orbitals which can accommodate electron pairs

Sadgwick suggested that electron pairs from ligands are added until the central
metal ion is surrounded by the same number of electrons as the next noble gas.

The total number of electrons which the central metal ion appears to possess
in the complex including those gained by it in bonding, is called the EAN

The effective atomic number should be equal to 36(electrons in krypton), 54

(electrons in xenon) or 86(electrons in Radon)
Effective Atomic Number (EAN) contd

Consider the complex ion [Co(NH3)6]3+

 the atomic number for cobalt is 27

The number of electrons for Co3+ is 24
6 ammonia molecules donate a pair of electrons each
 = 24+(2x6) = 36
This is the same as the atomic number of Krypton
Complexes that obey the EAN rule
(a) [Pd(NH3)6]4+

EAN = 54 = Xe

(b) [Co(NH3)6]3+

EAN = 36 = Kr

(c) [Fe(CO)5]

EAN = 36 = Kr
Complexes that do not obey the EAN rule

(a) [Pt(NH3)4]2+

EAN = 84

(b) [Fe(CN)6]3-

EAN = 35

(c) [Ni(NH3)6]2+

EAN = 38
Stability of complex ions
Stability of a complex is determined by its dissociation constant
Consider the following equation

[Ag(NH3)2)]+ Ag+ + 2NH3

Equilibrium constant K (or the dissociation constant) is given by the following

equation

K = [Ag+][NH3]2/[Ag(NH3)2]+

The smaller the value of the dissociation constant, the greater the stability of the
complex
Factors affecting the stability of a complex ion
(i) the nature of the ligand

(ii) the nature of the central ion

(iii) the chelate effect

Factors affecting the stability of a complex ion
(i) the nature of the ligand
The more basic the ligand, the greater the ability to donate electrons and the greater
the stability of the complex formed. For anionic ligand the smaller the ion and the
higher the charge, the more stable the complex formed.

(ii) the nature of the central ion

(iii) the chelate effect

Factors affecting the stability of a complex ion
(i) the nature of the ligand
The more basic the ligand, the greater the ability to donate electrons and the greater
the stability of the complex formed. For anionic ligand the smaller the ion and the
higher the charge, the more stable the complex formed.
(ii) the nature of the central ion
The greater the charge density of the central ion, the greater the stability of the
complex formed. The greater the electronegativity of the central ion the greater the
stability of the complex
(iii) the chelate effect
Factors affecting the stability of a complex ion
(i) the nature of the ligand
The more basic the ligand, the greater the ability to donate electrons and the greater
the stability of the complex formed. For anionic ligand the smaller the ion and the
higher the charge, the more stable the complex formed.
(ii) the nature of the central ion
The greater the charge density of the central ion, the greater the stability of the
complex formed. The greater the electronegativity of the central ion the greater the
stability of the complex
(iii) the chelate effect
chelating ligands are known to form more stable complexes than similar no
chelating ligands. This is known as the chelate effect.
Coordination numbers and geometries

The ligands adopt a definite geometry around a central metal ion, depending on
the coordination number of the ion

Ligands are arranged in a manner that minimizes repulsion

Coordination number 2

Two possible arrangements (i) linear (ii) bent

Linear - metal ion utilizes two hybrid orbitals and has no lone pair of electrons
Bent - metal ion utilizes two hybrid orbitals and has a lone pair of electrons

• Largely limited to d10 metal ions

for example, [CuCl2]- [Ag(NH3)2]+ ∠L-M-L ≈ 180°
Coordination numbers and geometries

• Bulky ligands may force 2-coordinate environment on metals that usually

prefer a greater number of ligands.
Coordination number 3

Complexes with coordination number 3 are rare

The geometry is trigonal planar or T-shaped

eg HgI3
Coordination number 4
Tetrahedral Square planar

 Square planar complex are also encountered but

 Common amongst complexes of transition as well
rarer than tetrahedral
as non transition elements
 Often associated with d8 (but not limited to)
configurations of metals belonging to the 4d-
 dominantly found in complexes that are overall and 5d-series (Rh+, Pd2+,Au3+, etc.)
neutral or anionic, or which have d or d electron
0 10

count

E.g. [CuX ] , [FeX ] and [CoX ] (X = halogen anion).

4
2−
4
2−
4
2−

RuO4, [CdCl ] 4
2‐
Coordination number 5

Less common than 4- or 6-coordinate complexes, but still widely found.

Complexes are normally either square-pyrimidal or trigonal bipyrimidal

square-pyramidal trigonal bipyramidal

Common for lighter, smaller metal ions, rare for heavier transition metals
Coordination number 6

Most common coordination type by far for d metals

Seen for all configurations from d0 to d10
Octahedral geometry by far the most common. A few examples of
trigonal prismatic geometry are also known.

trigonal prismatic

Octahedral
Factors affecting coordination number
Size of metal ion:
 2nd and 3rd row metals usually have higher CN’s than 1st row
metals

 Size of metal ion decreases as formal charge increases, e.g.

r(Fe3+) < r(Fe2+)

 High coordination numbers most likely with large metal ions

Factors affecting coordination number

Size of ligands:
 Bulky ligands usually result in low CN’s
because of steric hindrance

 High coordination numbers most likely

with small ligands.
Factors affecting coordination number

Electronic factors:
 Metals with large number of electrons usually form
complexes with low CN’s

If metal forms multiple bonds with ligands, low CN’s result
Isomerism in coordination compounds

A. Structural isomerism B. Stereo isomerism

1. Ionization isomerism 1. Geometrical
2. Hydrate isomerism 2. Optical
3. Coordination isomerism
4. Linkage isomerism
Structural isomerism - Linkage isomerism
Arises due to ligands containing two atoms that can donate electrons.
These ligands are known as ambidentate ligands – (NO2, NCS)

[Co(NO2)(NH3)5]Cl2 [Co(ONO)(NH3)5]Cl2
Pentaamminenitrito-Ncobalt(III) chloride Pentaamminenitrito-Ocobalt(III) chloride
Nitrito-N can also be referred to as nitro
Structural isomerism - Linkage isomerism

[Co(NCS)(NH3)5]Cl2 [Co(SCN)(NH3)5]Cl2
Pentaamminethiocyanato-Ncobalt(III) chloride Pentaamminethiocyanato-Scobalt(III) chloride
Thiocyanato-N can also be referred to as isothiocyanato
A. Structural isomerism- Ionization isomerism
Occurs when a ligand and a counterion in one compound exchange places

1. [CoBr(NH3)5]SO4 and [CoSO4(NH3)5]Br (Same empirical formula, but not the

same compound).

2.

Pentaamminechlorocobalt(III) bromide Pentaamminebromocobalt(III) chloride

A. Structural isomerism- Ionization isomerism

3.

Pentaaquachlorochromium(III) sulphate Pentaaquasulphatochromium(III) chloride

A. Structural isomerism- - Hydrate isomerism
Arises from the replacement of water by a ligand
1.

[Cr(H2O)6]Cl3 [CrCl(H2O)5]Cl2 • H2O

hexaaquachromium(III) chloride pentaaquachlorochromium(III) chloride
monohydrate

[CrCl2(H2O)4]Cl • 2H2O
Tetraaquadichlorochromium(III) chloride dehydrate – draw the structure of this isomer
2. Draw and name the following hydrate isomers; [Co(NH 3)5H2O](NO2)3 and [Co(NH3)5NO2](NO2)2 • H2O
B. Stereoisomerism - Geometrical isomers
Arises due to ligands occupying different positions around the metal ion

cis trans isomerism

cis form – on the same side trans form – opposite to one another

geometrical isomerism is not possible for complexes with coordination number

2 and 3 –

Geometrical isomerism of compounds with coordination number 4 and 6 is most

important
Geometrical isomers in complexes of coordination number 4

Coordination number 4 – tetrahedral or square planar geometries possible

Cis trans isomerism not possible in tetrahedral complexes, only in square planar

Complexes of the type Ma2b2 (Maabb) can exist as cis trans isomers
1. [PtCl2(NH3)2]

2. [Pd(NO2)2(NH3)2] – draw the cis and trans isomers of the compound

Geometrical isomers in complexes of coordination number 4
Complexes of the type Ma2bc (Maabc)
Cis trans isomerism is possible in complexes of the type Ma2bc
The two a groups can be adjacent (cis isomer) or opposite (trans isomer) to
each other

Example: [Pt(py)2NH3Cl] py=pyridine =

cis-[Pt(py)2NH3Cl] trans-[Pt(py)2NH3Cl]
Cl Cl
Geometrical isomers in complexes of coordination number 4

Complexes of the type M(ab)2

Where ab is a bidentate ligand with two different donor atoms

Can exist as cis trans isomers

For example [Pt(gly)2] where gly = NH2CH2COO-
Geometrical isomers in complexes of coordination number 4

No geometrical isomers for Complexes of the type Ma3b or Mab3

Geometrical isomers in complexes of coordination number 4
Complexes of the type Mabcd

Three possible geometrical isomers

Example: [Pt(NO2)(C5H5N)(NH3)(NH2OH)]+

Draw all possible isomers of the complex ion

Geometrical isomers in complexes of coordination number 6

Coordination number 6 – octahedral geometry

Complexes of the type Ma4b2, Ma2b4, Ma4bc show geometrical isomerism
Example [CoCl2 (NH3)4]+ can exist as cis trans isomerism
Draw the isomers
Geometrical isomers in complexes of coordination number 6
[CoCl2 (NH3)4]+
Which one is trans and which one is cis?
Geometrical isomers in complexes of coordination number 6
Complexes of the type Ma3b3

For a complex having the general formula [Ma3b3] there are two ways of
arranging the ligands, either facial (fac) or meridional (mer).

mer isomer has each of one type of ligand (A) lying in a

plane that includes the metal, at right-angles to the plane
fac carries 3 A ligands in an equilateral of the other type of ligand (B).
triangle on one face of the octahedron,
and 3 B ligands on the other face:

Example [RhCl3(py)3]
Geometrical isomers in complexes of coordination number 6

Complexes of the type M(aa)2b2

Where aa is a bidentate ligand and b2 represent two identical ligands
Example: dichlorobis(ethylenediamine)cobalt(II) chloride en =
-write down the IUPAC formula
[CoCl2(en)2]Cl
-Draw isomers of the complex ion
(a) cis (b)
trans
(c)
Geometrical isomers in complexes of coordination number 6

Complexes of the type M(aa)2b2

Example 2: Potassium diaquabis(oxalato)chromate(III)
- Give the UPAC formula of the compound
K[Cr(C2O4)2(H2O)2]
- Write down the formula of the complex ion
Oxalato
- [Cr(C2O4)2(H2O)2]-
Draw the isomers of the complex ion
Geometrical isomers in complexes of coordination number 6

Complexes of the type M(aa)2bc

Where aa is a bidentate ligand, and b and c are two different monodentate
ligands.
Example 1: chlorocyanobis(ethylenediamine)cobalt(III) chloride
Write down the IUPAC formula for this compound
- [CoClCN(en)2]Cl
Draw the isomers of the complex ion
cis trans
CN CN CN
Geometrical isomers in complexes of coordination number 6

Complexes of the type Mabcdef

Metal salt is attached to six different ligands

Mabcdef complexes are possible, but uncommon

Optical isomerism
Compounds that rotate the plane of polarized light are known as optically active
substances

Optically active isomers which rotate the plane of polarized light equally but in
opposite direction are called enantiomers

Dextro rotatory (d) – rotate plane of polarized light to the right

Laevo rotatory (l) - rotate plane of polarized light to the left

The d and l are mirror images of each other

- Optically active compounds should not have a centre of symmetry

A pair of enantiomers consists of two molecular species
which are nonsuperimposable mirror images of each
other
Optical isomerism in coordination complexes

Optical isomerism in possible in coordination complexes of coordination number 4

and coordination number 6

For coordination number 4, optical isomerism is only possible in

tetrahedral complexes

For coordination number six, optical isomerism is possible in complexes of the type

- [M(aa)3]
- [M(aa)2b2] or [Mb2(aa)2] and
- [M(aa)2bc] or [Mbc(aa)2]
Optical isomerism in complexes with coordination number 4
• Square planar complexes are seldom optically active

• Tetrahedral complexes exhibit optical isomerism – for example [CoBrClINH 3]-

The enantiomers are non-

super imposable mirror images

Mirror plane
Optical isomers in metal complexes with coordination number 6

• Complexes of the type [M(aa)3] where aa is a bidentate ligand exhibit

optical isomerism.

Example 1: [Co(en)3]3+

Non superimposable mirror images

Optical isomers in metal complexes with coordination number 6

• Complexes of the type [M(aa)3] where aa is a bidentate ligand exhibit

optical isomerism.

Example 2: K3[Fe(C2O4)3] or K3[Fe(ox)3]

Give the name of the compound and draw the isomers
Potassium tris(oxalato)ferrate(III)
Optical isomers in metal complexes with coordination number 6

• Complexes of the type [M(aa)2b2] or [Mb2(aa)2] where aa is a bidentate

ligand and b is a monodentate ligand.

Example: [CoCl2(en)2]Cl
By now you know that [CoCl2(en)2]Cl exhibits cis/trans isomerim
Only the cis isomer is optically active
Superimposable mirror images not
Non superimposable mirror images optically active
Cis isomer Optically active trans isomer
Optical isomers in metal complexes with coordination number 6

• Complexes of the type [M(aa)2bc] or [Mbc(aa)2] where aa is a bidentate

ligand and, b and c are monodentate ligands.

Example: [CoClCN(en)2]Cl
exhibits cis/trans isomerim
Only the cis isomer is optically active
Superimposable mirror images not
Non superimposable mirror images optically active
Cis isomer Optically active trans isomer

CN CN CN CN
The end