CHM361

CHAPTER 5:

COORDINATION COMPOUND
 LEARNING OUTCOMES

1) Apply the knowledge of electron configuration of transition

metals and ligand structures to name and determine the
geometry, isomerism and hybridization of coordination
compounds.

2) Conduct, observe and report scientific investigation in

selected areas of inorganic and coordination chemistry.
 COORDINATION COMPOUNDS

 Ligands
 Complex Ions
 Coordination Number
 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

 Species where transition metal ion is surrounded by a

certain number of ligands.

Complex ion

[Co(NH3)5Cl]Cl2 Counter ion

Metal atom ligand

 LIGANDS

 Molecules or ions that surround the metal in a complex ions.

Complex ion

[Co(NH3)5Cl]Cl2 Counter ion

Metal atom ligand

 Ligands as a Lewis base : donating 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 atom

bidentate : two donor atoms
polydentate : more than two donor atoms
[tetradentate (4), pentadentate (5),
hexadentate (6) ……..]
 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
SOME COMMON LIGANDS
 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.
Cation & Anion (Counter Ion)
CATION FORMULA ANION FORMULA ANION FORMULA

Aluminum Al+3 Fluoride F- Hypochlorite OCl-

Ammonium NH4+ Chloride Cl- Nitride N3-

Barium Ba+2 Bromide Br- Carbonate CO32-

Hydrogen carbonate
Calcium Ca+2 Iodide I- HCO3-
or Bicarbonate

Lead(II) Pb+2 Sulfate SO42- Amide NH2-

Lithium Li+ Hydrogen sulfate HSO4- Chromate CrO42-

Magnesium Mg+2 Thiosulfate S2O32- Dichromate Cr2O72-

Nitronium NO2+ Sulfite SO32- Iodate IO3-

Potassium K+ Sulfide S2- Bromate BrO3-

Sodium Na+ Perchlorate ClO4- Nitrate NO3-

Strontium Sr+2 Chlorate ClO3- Nitrite NO2-

Zinc Zn+2 Chlorite ClO2-

 NOMENCLATURE

3) Names of ligands:

 anionic ligands end with “o”.

 Neutral ligands usually called by the name of the molecule.

 Exception for H2O, CO, & NH3

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
SO42- sulphato P(C6H5) 3 Triphenylphosphine
C2O42- oxalato C5H5N pyridine
CO32- carbonato
CH3COO- acetato
NH2- amido
NH2- imido
-
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…

 Prefix are ignored when alphabetizing ligands.
eg: [Co(NH3)4Cl2]+ = tetraamminedichloro

 For polydentate ligands, use prefix bis (2), tris (3), tetrakis (4)
 eg: (en)2 = bis(ethylenediamine)
 NOMENCLATURE

4) Oxidation number of metal is written in roman (I, II, III) following the
name of the metal.

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

5) 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 Argentate
Au Gold /Aurum Aurate
Sn Tin Stannate
Al Aluminium Aluminate
Pt Platinum Platinate
 Example

cation anion

[Cr(NH3)3(H2O)3]Cl3

1) Oxidation no of metal:
Cr + 0 + 0 + (-1 x 3) = 0
Cr = +3

2) Complex ion : triamminetriaquachromium (III)

2) Counter ion : chloride

3) Name: triamminetriaquachromium (III) chloride

 Example

cation anion

K4[Fe(CN)6]
1) Oxidation no of metal:
(1 x 4) + Fe + (-1 x 6) = 0
Fe = +2

2) Complex ion : hexacyanoferrate (II)

3) Counter ion : potassium

4) Name: potassium hexacyanoferrate (II)

 EXERCISE 1

Write the systematic name for the following:

1. K2[FeCl4]

2. [Pd(NH3)3Cl]+

3. K4[Fe(CN)6]

4. [Co(en)2Cl2]NO3

5. (NH4)2[Pt(NH3)2Br4]

6. [Cr(en)2(SCN)2]+
 EXERCISE 2

Write formula name for the following:

1) Tetraaquadibromocobalt(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 are tetrahedral.
 STRUCTURE

d electron Ligand Structure

d7, d8, d9 Strong Square planar

d7, d8, d9 Weak Tetrahedral

d4 Strong Tetrahedral

d4 Weak Square planar

2nd & 3rd period Square planar

Irrespective types of
Cu+ ligands Tetrahedral

Cu2+ Square planar

Mn2+ Tetrahedral
 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 STREOISOMER
between atoms spatial arrangement

COORDINATION
HYDRATE IONIZATION LINKAGE GEOMETRIC OPTICAL
SPHERE
 STRUCTURAL ISOMER
(HYDRATE)
Coordination compound that have the same composition but differ in the
number of water molecules present as ligands.
 STRUCTURAL ISOMER
(IONIZATION)
Two coordination compounds in which two different anions switch
positions between the inner and outer coordination sphere.
 STRUCTURAL ISOMER
(LINKAGE)
Coordination compound having the same complex ion structure but differ in
donor atom attachment.

[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]

 STEREOISOMER (GEOMETRIC)

 Streoisomers that cannot be converted without breaking a chemical bond.

 Comes in pair.

 Use term cis & trans.

 Cis = two groups of atoms are adjacent to each other.

 Trans = two groups of atoms are on opposite side to each other.

 Only square planar (4) & octahedral (6) have geometrical isomer.

 Generally have different colors, melting points, & chemical reactivities.

 STREOISOMER (GEOMETRIC)

 ammonias and the  ammonias and so are the

chlorines are next door to chlorines are arranged opposite
each other. each other.
 STREOISOMER (GEOMETRIC)

 chlorines are next door  chlorines are arranged

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

 Coordination compounds that are mirror images & non-superimposable to each

other.

 Comes in pair.

 Have identical physical & chemical properties.

 Chiral molecule = nonsuperimposable with their mirror images.

 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

NON SUPERIMPOSE CIS ISOMER

NON SUPERIMPOSE

TRANS ISOMER
SUPERIMPOSE