Royal College of Surgeons in Ireland - Medical University of Bahrain

MCP 03.12 Coordination Chemistry II

 Learning outcomes

• Define ligand denticity and provide examples for common

mono- and polydentate ligands

• Name and write chemical formulas for coordination

compounds follow IUPAC method

• Define chelating agent and chelate

• Explain the relationship between ring size and chelate

stability

• Explain the high stability of a metal-EDTA complex

 Coordination chemistry
Coordination compounds contain two simpler compounds; usually
complex and counter ion.

A complex is any species involving coordinate bonding of groups

(ions or molecules), termed ligands, to a metal (atom or ion).
Coordination Counter
sphere ion

+3 0 -1
[Co(NH3)4Cl2]+1 Cl

Central metal cation; Ligands;

LA LB
Electron pair accepted Electron pair donor
 Coordination chemistry

Primary valence
Charge on. complex = ΣOxidation no. of metal and ligands

Secondary valence
Coordination number = ΣDonor atoms around central metal in the
complex

[Co(NH3)4Cl2]Cl

Primary valence Secondary Valence

+3 6
Coordination chemistry – geometries
(recap)
Oxidation state on The charge on a metal 2+
metal ion complex ion NH3
2+
Zn
+ NH3
H3N NH3
H3N Ag+ NH3

Tetrahedral
Linear
C.N. = 2 C.N. = 4
Ideal bond angle = 180o Ideal bond angle = 109.5o
3+
2+ NH3
H3N NH3 H3N NH3
3+
Pt 2+ Co
H3N NH3
H3N NH3 NH3

Square Planar Octahedral

C.N. = 4 C.N. = 6
Ideal bond angle = 90 and 180o Ideal bond angle = 90 and 180o
 Naming metal complexes
1. The cation is named before the anion.

K3[Fe(CN)6] [Co(NH3)4Cl2]Cl

[Co(NH3)4Cl2]Cl Complex before Cl

2. Within the complex ion, the ligands are named first in alphabetical
order and the metal last.

3. Ionic ligands end with “o”; Bromo, fluoro. Neutral ligands are usually
named after the molecule. Exceptions include H 2O (aqua), CO
(carbonyl) and NH3 (ammine).
Coordination chemistry
Coordination chemistry
 Naming metal complexes

4. With several ligands of the same kind, the prefixes di-, tri-, tetra-,
penta-, hexa- are used. If the prefix is already included in the name,
bis(2), tris(3) and tetrakis(4) is used.

[Co(NH3)4Cl2]Cl Tetraamminedichloro

[Cr(en)3]Cl3 Tris(ethylenediamine)

5. The oxidation number of the metal is written in roman numerals

following the metal.

[Co(NH3)4Cl2]Cl Cobalt(III)
 Naming metal complexes
6. If the complex is an anion, the ending –ate is attached to the metal.
For some metals the English name is replaced by the Latin name.

[Fe(CN)6]4- Ferrate

Final names
[Co(NH3)4Cl2]Cl
Tetraamminedichlorocobalt(III) chloride

K3[Fe(CN)6]
Potassium Hexacyanoferrate(III)
 Question

Which of the following is the name of the coordination compound

[Co(NH3)5(ONO)]Cl2?

A. Amminenitrito-O-cobalt(III) fluoride
B. Chloride pentaamminenitrito-O-cobalt(III)
C. Nitrito-O-pentaamminecobalt(III) chloride
D. Pentaamminenitrito-N-cobalt(III) chloride
E. Pentaamminenitrito-O-cobalt(III) chloride
 Writing formula of metal complexes

1. Cations are written before anions.

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

2. The ligands are listed in alphabetical order, regardless of their

charge, based on their name as per IUPAC 2004.

Tetraaminechloronitrito-N-cobalt(III) chloride
4 NH3 Cl- NO2-
[Co(NH3)4Cl(NO2)]Cl
 Question

Which of the following is the formula for the coordination

compound Pentaamminechlorocobalt(III) chloride?

A. [ClCo(NH3)5]Cl2
B. [Co(NH3)5Cl]
C. [Co(NO)5Cl]Cl
D. Cl2[Co(NH3)5Cl]
E. [Co(NH3)5Cl]Cl2
 Ligand denticity - monodentate

A monodentate ligand can donate one electron pair to a metal in a

complex.

Donated pairs of electrons cannot be on the same atom.

 Ligand denticity - monodentate
Some monodentate ligands that have more than one
lone pair of electrons can act as bridging ligands.

4+
Hydroxide ion
OH2 OH2
H
H2O O OH2
Fe Fe
H2O O OH2
- H
OH O O
H2 H2

{(Fe(III)(OH2)4)2(µ-OH)}2
The Greek symbol 'mu', μ, precedes the bridging ligand. It
itself is preceded by a superscript number denoting the
number of metals bound to the bridging ligand. Note μ2 is
often denoted simply as μ.
 Ligand denticity - polydentate
Polydenate ligands have more than one electron pair in the ligand
to bind to the central metal.

The donated lone pairs must be on different atoms in the ligand.

Lone pairs on a polydentate ligand must be far enough apart to

attach to the metal centre at two or more points and that bind to
different sites in the geometric structure of a complex.
Ligand denticity – bidentate (2)

O O
Donor atoms
C C H2C CH2

O O H2 N NH2
- -
Ox2- en
oxalato ethylenediamine

H2
N O O
H2C 2+ C
Pt
H2C C
N O O
H2

Pten(ox)
 Ligand denticity – tetradentate
(4)

H2 H2 H2 H2
H2C C C C C CH2
Donor
H2N N NH2 atoms
H N
H

Triethylenetetraamine
 Ligand denticity – hexadentate
(6)

O O
- H2 H2 C CH2 -
O C C CH2 C O
N N
Donor atoms O C C H2C C O
- H2 -
O O
Edta4-
Ethylenediaminetetraacetato
 Chelating agents

When the bonding of a polydentate ligand to a metal ion produces

a ring, we refer to the complex as a chelate, the ligand as the
chelating agent, and the process of chelate formation chelation.

2+
NH2 H
2
H2N N
Ni 5-
HN N membered
N H2 ring
H2

[Ni(en)3]2+
 Chelating stability

Complex ions with polydentate ligands are typically a lot more

stable than those with monodentate ligands – they have
higher stability constants.
2+ 2+
NH2 H NH3
2
H2 N N H3N NH3
Ni Vs Ni
HN N H3N NH3
N H2
N
H2 H3

[Ni(en)3]2+ [Ni(NH3)6]2+
Stability
1.1 x 1018 5.3 x 108
Constant
Chelating stability

The order of stability depends on ring size.

A 3-membered ring is very strained (bond angles 60o),

A 4-membered ring is quite strained (bond angles 90o).

Bigger rings (7-, 8- etc.) are floppy.

3 < < < 4 < < 5 > 6 >> 7 >> 8

 EDTA

H4EDTA, ethylenediamminotetraacetic acid, is an important

hexadentate chelating agent.
It can be used to remove or sequester unwanted cations or
metals from solutions or in the case of metal poisoning.
Generally its used as a water soluble sodium salt.
O O O O 4-
H2 H2C CH2 H2 H2C CH2
HO C C CH2 C OH O C C CH2 C O
N N +
4Na N N
HO C C H2C C OH O C C H2C C O
H2 H2
O O O O

H4EDTA Na4EDTA

The fully deprotonated ligand is EDTA4- and therefore

the net charge on the ligand is -4.
 EDTA
It forms highly stable complexes with Ca2+, Mg2+, Fe2+ and
Fe3+, Co3+ and Pb2+.
If the central metal ion, M, has an oxidation number of n+ the
overall charge on the complex is + n - 4.
 Question

Draw the structure of diaquabis(ethylenediamine)nickel(II).

 Learning outcomes

• Define ligand denticity and provide examples for common

mono- and polydentate ligands

• Name and write chemical formulas for coordination

compounds follow IUPAC method

• Define chelating agent and chelate

• Explain the relationship between ring size and chelate

stability

• Explain the high stability of a metal-EDTA complex