What is a coordination compound?

• Coordination compounds are all compounds where a metal is

covalently bonded to other atoms, ions or molecules .

• There is a clear distinction between groups which are bonded to

metals, and those that are needed to neutralize charge of
complex ions.

• Example. [Co(NH3)4Cl2]CN is not the same as [Co(NH3)4ClCN]Cl

Þ The ligands inside the block brackets are covalently bonded

and are part of the coordination sphere of the cobalt
complex.

Þ CN- or Cl– is outside the coordination sphere.

 Ligands outside the coordination sphere

[MX4Y2]Z2
Metal cation

Ligands bond covalently to metal cation

Atoms, ions or molecules

 [MX4Y2] [MX4Y2]Z2 Z2[MX4Y2]

Neutral complex Complex ion with

negative charge
Complex ion with
positive charge
 [MX4Y2]Z2

Complex ion with positive charge

negative

[M X4Y2]
n+ (n-2(charge of Y))+
neutral

Example: [Co(NH3)4Cl2]CN
[Co(NH3)4Cl2]CN
3.1 Naming of coordination compound

• Coordination compound consists of:

• Central atom

• Metal atom (M)

• Bond with more atoms (B) or groups (C) than is M possible

with OT

• M has empty orbitals - electrons are donated by other

atoms or groups

• Ligands

• Atoms (B) or groups of atoms (C)

• Have electron pairs for coordinative covalent bond

Ligands

• Monodentate

• Forms coordinative covalent bond with one of its atoms

Example. R3N, Cl-

• Bridged compounds

• atoms form coordinative compound with two different atoms

Example
• Polydentate

• more than one potential coordinating atom

Example

• Chelate

• two or more coordinative bonds with the same central atom

Þ ring structure
Example
3.1.1 Notation (MFT320)

• In formula:
• Symbol of the central atom normally first

• Earlier :
Anionic ligand first, followed by neutral and cationic ligands

• New convention :
Everything alphabetically if the number of prefixes like bi- and tri-
are ignored

• The formula of the whole complex entity are placed in block

brackets.

• In name:
With the name, the ligands are named first and the metals last
3.1.2 Anionic (negative) ligands

• Anionic ligands have names ending with a -o

Example. chloro (Cl-), hydroxo (OH-), sulphato (SO42-); amido

(NH2-), imido (NH-)

NO2-:
Þ coordinated by nitrogen
- nitro - Nitrito-N
Þ coordinated by oxygen
- nitrito - Nitrito-O

SCN-
Þ coordinated by nitrogen
- thiocyanato-N
Þ coordinated by sulphur
- thiocyanato-S
The sequence is :

1. H- (hydride), hydrido

2. O2- (oxide), oxo

3. OH- (hydroxide), hydroxo

4. Simple mono-atomic inorganic anions in alphabetic order

5. Poly-atomic inorganic anions in alphabetical order

6. Organic anions in alphabetic order

3.1.3 Neutral ligands

• Naming is non-systematic.

• In most cases the name of the coordinating molecule is left

unchanged.

• Some of the more common molecules have special names

Example. H2O (aqua), NH3 (ammine), NO (nitrosyl), CO (carbonyl)

NB: RNH2
ammine - inorganic
amine - organic
3.1.4 Cationic (positive) ligands

• Cationic ligands have names ending with –ium.

Example. NH4+ (ammonium),

NO+ (nitrosonium)
3.1.5 Coordination compounds with one central atom

1. The cation is named first if the compound is ionic.

2. In the coordination compound the ligands and the metals are given
according to the rules.

3. Stock-notation :
The oxidation state of the central metal is indicated by Roman
numerals in brackets (oxidation state 0 is used as well).

Ewing-Basset notation:
The charge of the complex in the square brackets, is written in
arabic numerals behind the metal in the brackets.
4. If the complex ion is an anion, the suffix –ate is added to the name
of the metal.

5. The number of the ligand of the same type are indicated by the
prefix di-, tri-, tetra-, penta, hexa-, hepta-, octa-, ........

Examples:

[Co(NH3)6]Cl3 Stock notasie

hexa-ammine cobalt(III) chloride
hexa-ammine cobalt(3+) chloride

K[Co(CN)(CO)2(NO)] Ewing-Basset-notasie

potassium cyano dicarbonyl nitrosyl cobaltate(0)

potassium cyano dicarbonyl nitrosyl cobaltate(1-)

[CrCl(NO2)(NH3)4]NO3
chloro nitro tetrammine chrome(III) nitrate
chloro nitro tetrammine chrome(1+) nitrate
3.1.6 Complex ligands

• Ligands with confusing long names are placed in brackets.

• Numerical prefix – number of ligands

• bis-, tris-, tetrakis-, pentakis-, heksakis-, .......

• Example
• K3[Al(C2O4)3]
potassium tris oxalato-aluminate(III)
potassium trisoxalato-aluminate(3-)

• [Co(en)3]Cl3
• (en) = ethylenediamine
tris(ethylenediamine) cobalt(III) chloride

• Ni(PF3)4
tetrakis(phosfor(III) fluoride) nickel(0)
3.1.7 Bridged ligands

• Bridged ligands are indicated by  in front of the name.

• Example

Bis(ethylenediamine) cobalt(III) -hidroxo -imido bis(ethylenediamine) cobalt(III) chloride

3.1.8 Geometric and optic isomers

• cis- or trans- prefixes.

• Example
• [Cr(H2O)4Cl2]Cl

OH2

Cl

trans-dichloro tetra-aqua chrome(III) chloride

Assignment:
Do exercises 9.1 and 9.2 MFT321