CHAPTER 5

COORDINATION COMPOUND

FACULTY O F A P P L I E D S C I E N C E S
U i TM PAHANG
 OUTLINES
• Ligands
• ComplexIons
• CoordinationNumber
• Nomenclature
• Isomerism
 Structural isomerism ( hydrate, ionization,
linkage and coordination sphere)
 Stereoisomerism (geometric and optical)
 COORDINATION COMPOUNDS

 Compound that typically consist of a complex ion and

counter ion.

 Most but not all, of the metals in coordination

compounds are transition metal.

Complex ion

[Co(NH3)5Cl]Cl2 Counter ion

Can be cation or anion
 COMPLEX ION

Complex ion : [Metal cation + ligand]

Species where transition metal ion is surrounded by a

certain number of ligands.

Complex ion

[Co(NH3)5Cl]Cl2 Counter ion

Metal atom ligand

 A coordination compound behaves like an electrolyte in water: the

complex ion and counter ion separate from each other.

H2O
[Co(NH3)6Cl3(s) [Co(NH3)6]3+(aq) + 3Cl- (aq)

 However, the complex ion behave like polyatomic ion: the ligands and

central metal ion remain attached.

 LIGANDS

 Molecules or ions that surround the metal in a complex ions,

 A ligand has at least one unshared pair of valence electrons.
Complex ion

[Co(NH3)5Cl]Cl2 Counter ion

Metal atom ligand

 Ligands as a Lewis base : donating a pair of electrons.
 Transition metal as a Lewis acid : accepting a pair of electron from Lewis
base.
 LIGANDS

 Depending on the number of donor atoms present.

 Ligands are classified as:

Monodentate : one donor atoms

Bidentate : two donor atoms

Polydentate : more than two donor atoms

[tetradentate (4), pentadentate (5), hexadentate (6)]
SOME COMMON LIGANDS
 Bidentate and Polydentate Ligands

 It causes ‘rings” in the complex ion.

 It appears to grasp the metal between two or more donor atoms,

thus, these ligands are also known as chelating ligand (chelating
agent).

 A complex ion that contain these ligands is called a chelate

(pronounce KEY-late).

 Chelatingligands more stable complex that do related

monodentate ligands.
I) Bidentateligand
I. Bidentate Ligands
II. Polydentate Ligands (EDTA)
 COORDINATION NUMBER

 Number of donor atoms surrounding the central metal atom in a

complex ion.
 Donor atoms : atom in a ligand that is bound directly to the metal
atom.
Complex ion

[Co(NH3)5Cl]Cl2 Counter ion

Metal atom ligand

 Atom in ligand that bound directly to Co metal atom is N & Cl.
 N & Cl are donor atom.
 Number of N = 5, Number of Cl = 1
 Coordination number = 6
 COORDINATION NUMBER

Complex ion Metal Ligands Coordination no.

Cation
(no. of

bonds)

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

[Cu(H2O)4]2+ Cu2+ 4 H2O molecules 4

[Fe(CN)6]3- Fe3+ 6 CN- ions 6

Find coordination number for compound K4[Mn(C2O4)2(CN)2]:

-4

NC

Mn

NC

Answer: 6
 CHARGE OF COMPLEX IONS

… is the sum of the charges on the central metal and on its

surrounding ligands.

For example in [Cu(NH3)4]SO4,

Counter ion SO4 has a 2- charge.
So, the complex ion must have a 2+ charge, [Cu(NH3)4]2+

Use the charge of the complex ion to calculate the oxidation

number of Cu.
NH3 ligands are neutral molecules,
The oxidation number of Cu:
[Cu(NH3)4]2+
Cu+4(0)= + 2
 NOMENCLATURE

1) Cation is named before the anion.

cation anion

K3 [Fe(CN)6] = K+ is named first

cation anion

[Cr(NH3)3(H2O)3] Cl3 = Cr(NH3)3(H2O)3 is named first

2) Within complex ion, ligands are named first, in alphabetical order,

and metal ion is named last.
 NOMENCLATURE

3) Names of ligands:
 Anionic ligands end with “o”.

 Neutral ligands usually called by the name of the

molecule.

 Exception for H2O, CO, and NH3

NAME OF SOME COMMON LIGAND
Anionic Ligands Names in Neutral Ligands Names in
complexes complexes

Bromide, Br- bromo Ammonia, NH3 ammine

Flouride, F- fluoro Water, H2O aqua

Oxide, O2- oxo Nitro, NO Nitrosyl

Hydroxide, OH- Hydroxo Carbon Monoxide, Carbonyl

CO
Cyanide, CN- cyano Oxide, O2 dioxygen

Oxalate, C2O42- oxalato Nitrogen, N2 dinitrogen

Carbonate, CO 2-
3 carbonato Pyridine, C5H5N pyridine

Acetate, acetato H2NCH2CH2NH2 ethylenediamine

CH3COO-
Azide, N3- Azido
Names of ligands: ANIONIC LIGAND NEUTRAL LIGAND
LIGANDS NAMES LIGANDS NAMES
Br- bromo NH3 ammine
Cl- chloro H2O aqua
I- iodo NO Nitrosyl
F- fluoro CO Carbonyl
CN- cyano O2 dioxygen
OH- Hydroxo N2 dinitrogen
O2- oxo H2NCH2CH2NH2 ethylenediamine

sulphato P(C6H5)3 Triphenylphosphine

SO42-
C2O42- oxalato C5H5N pyridine
CO32- carbonato

CH3COO- acetato

NH2- amido
imido
NH2-
ONO- (O-bonded) nitrito
NO2- (N-bonded) Nitro

SCN- (S-bonded) Thiocyanato

NCS- (N-bonded) Isothiocyanato
gly- glycinato
N3 - azido
 NOMENCLATURE

4) If more than one ligands present, use prefix.

 di, tri, tetra, penta, hexa, hepta…
 Prefix are ignored when alphabetizing ligands.
ex: [Co(NH3)4Cl2]+ = tetraamminedichloro

 For bidentate and polydentate ligands, use prefix

bis (2), tris (3), tetrakis (4)

ex: (en)2 = bis(ethylenediamine)

NUMERICAL PREFIX

Number Prefix Number Prefix Number Prefix

1 mono 5 Penta 9 Nona
(pentakis) (ennea)

2 di (bis) 6 Hexa 10 deca

(hexakis)

3 tri (tris) 7 hepta 11 undeca

4 Tetra 8 octa 12 dodeca

(tetrakis)
 NOMENCLATURE

5) Oxidation number of metal is written in roman (I, II, III)

following the name of the metal.

Example: [Cr(NH3)4Cl2]+ = chromium (III)

6) If complex ion is a cation, the metal is named same as

the element. But, If complex ion is an anion, the name of
the metal ends with the suffix – ate.

Example: [Fe(CN)6]4- = hexacyanoferrate (II) ion

Transition Metal Name if in Cationic Name if in Anionic
Complex Complex

Sc Scandium Scandate
Ti Titanium Titanate
V Vanadium Vanadate
Cr Chromium Chromate
Mn Manganese Manganate
Fe Iron Ferrate
Co Cobalt Cobaltate
Ni Nickel Nickelate
Cu Copper Cuprate
Zn Zinc Zincate
Pb Lead Plumbate
Ag Silver Argenate
Au Gold /Aurum Aurate
Sn Tin Stannate
Al Aluminium Aluminate
Pt Platinum Platinate
 Complex ion as cation
2

1) Name cation first then anion. Identify which is anion and cation.
Cation Anion
[Co(NH3)5Cl]2+ Cl-
2) In complex ion Ligand are named before the metal. Ligand list in
alphabet order. (Anion ligands end in “o”)
Thus in [Co(NH3)5Cl]2+ we name ammonia first followed by chloride and
then metal cation (cobalt)
amminechlorocobalt
3) Fill the greek prefixed indicate the number of ligand
5 NH3 = penta,
Pentaamminechlorocobalt
4) Oxidation state give to parentheses in Roman numeral following name
of metal
Pentaamminechlorocobalt(III)
5) Full name
Pentaamminechlorocobalt(III) Chloride
 Complex ion as anion

1) Name cation first then anion. Identify which is anion and cation.
Cation Anion
K+ [Fe(CN)6]3-
2) In complex ion Ligand are named before the metal. Ligand list in
alphabet order. (Anion ligands end in “o”). For complex ion is an anion, the
name of the central metal ended with suffix –ate
Thus in [Fe(CN)6]3- we name cyanide first followed by metal cation
(ferrate)
cyanoferrate
3) Fill the greek prefixed indicate the number of ligand
6 CN6 = hexa,
hexacyanoferrate
4) Oxidation state give to parentheses in Roman numeral following name
of metal
hexacyanoferrate(III)
5) Full name
Potassium hexacyanoferrate(III)
 EXERCISE 1

Write the systematic name for the following:

1) [Cr(NH3)3(H2O)3]Cl3
2) [Pt(NH3)5Cl]Br3
3) [Pt(H2NCH2CH2NH2)2Cl2]Cl2
4) Na2[NiCl4]
5) K2[Co(NH3)2Cl4]
6) [Co(NH3)4Cl2]Cl
7) [Cr(H2O)4Cl2]Cl
 EXERCISE 1

Write the systematic name for the following:

1) [Cr(H2O)5Cl]Cl2
2) K3[Fe(CN)6]
3) Na2[PtCl4]
4) [Mn(CO)(NH3)5]SO4
5) [Co(H2NCH2CH2NH2)3]2(SO4)3
6) K4[Fe(CN)6]
 EXERCISE 1

Write the systematic name for the following:

1) [Fe(CO)5]
2) (NH4)2[Ni(C2O4)2(H2O)2]
3) [Ag(NH3)2][Ag(CN)2]
4) [CoBr(NH3)5]SO4
5) [Fe(NH3)6][Cr(CN)6]
6) [Co(SO4)(NH3)5]+
7) [Fe(OH)(H2O)5]2+
 EXERCISE 2

Write formula name for the following:

1) Tetraaquodibromocobalt(III) nitrate
2) Tetracyanonickelate(II) ion
3) Tetraammineaquabromocobalt(III) bromide
4) Hexamminechromium(III) tetrachlorocuprate(II)
5) Pentaaquacyanoiron(III) chloride
6) Tetrahydroxocuprate(II) ion
 STRUCTURE

 Coordination number will determine the structure of the coordination

compounds.

COORDINATION NUMBER STRUCTURE

2 Linear
Tetrahedral
4
Square planar
6 Octahedral

 Four-coordinate platinum(II) complexes are always square planar.

 Whereas 4-coordinate cobalt(II) complexes aretetrahedral.

 6-co-ordinated complex ions

 Four of the ligands are in one plane, with the fifth one above the
plane, and the sixth one below the plane.
4-co-ordinated complex ions

Tetrahedral arrangement Square Planar arrangement

 ISOMERISM

 Compounds with same formula but different atom arrangement.

 There is more than one way to arrange ligands around the central atom.
 Will have distinctly different physical and chemical properties.

ISOMER

Compounds with Compounds with same

different connections STRUCTURAL connectivity but different STEREOISOMER
between atoms spatial arrangement

GEOMETRIC OPTICAL
COORDINATION
HYDRATE IONIZATION LINKAGE SPHERE DIASTEREOISOMERS ENANTIOMERS
 STRUCTURAL ISOMER
(HYDRATE)
Coordination compound that have the same composition but
differ in the number of water molecules present as ligands.
 Three isomers of CrCl3(H2O)6 are:

 The violet compound: [Cr(H2O)6]Cl3

 The blue-green compound: [Cr(H2O)5Cl]Cl2.H2O

 The green compound: [Cr(H2O)4Cl2]Cl.2H2O

These isomers have

different properties
(colour)
 STRUCTURAL ISOMER
(IONIZATION)
Two coordination compounds in which two different anions switch
positions between the inner and outer coordinationsphere.
 STRUCTURAL ISOMER
(LINKAGE)
Coordination compound having the same complex ion structure but
differ in donor atom attachment.
Nitrito isomer
Nitro isomer

[Co(NH3)5(NO2)]Cl [Co(NH3)5(ONO)]Cl
 STRUCTURAL ISOMER
(COORDINATION)

Coordination compound having the same composition but

occur through exchange of ligands between complex ion in the
same coordination compound
[Co(NH3)6] [Cr(C2O4)3] & [Co(C2O4)3] [Cr(NH3)6]
[Co(NH3)6] [Cr(CN)6] & [Co(CN)6] [Cr(NH3)6]
 STEREOISOMER

Compound have the same chemical formula and

bonding arrangement but differing in the spatial
arrangement of the atoms.

Two kind of stereoisomers:

a) Geometric isomers (Diastereoisomers)
b) Optical isomers (Enantiomers)
 STEREOISOMER
(GEOMETRIC)

 Stereoisomers in which the arrangement of constituent atoms

(ligands) is different through the same bonds are present.
 cis isomers
 trans isomers.

 Only square planar (4) & octahedral (6) have geometrical isomer.
 Cis-trans isomers are not observed in tetrahedral complexes
 Generally have different colors, melting points, & chemical
reactivities.
 STEREOISOMER
(GEOMETRIC)

• Ammonia and chlorine • Ammonia and chlorine are

are next to each other. arranged opposite each
other.
Cis isomers have identical Trans isomers have the identical
ligands in adjacent corner (same ligands in across the corner
side) of a square: (opposite side) of a square
 STEREOISOMER
(GEOMETRIC)

 chlorines are next to  chlorines are arranged

each other. opposite each other.
STEREOISOMER
(OPTICAL)
 STEREOISOMER
(OPTICAL)

 Optical isomers are possible for both tetrahedral

and octahedral complexes, but not square
planar.

 Only cis isomer can have optical isomer.

CIS ISOMER TRANS ISOMER
NON SUPERIMPOSE SUPERIMPOSE

CIS ISOMER
TRANS ISOMER NON SUPERIMPOSE
SUPERIMPOSE
 THE END…
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