Organic and Inorganic Chemistry

Week 6
Dr. Humayun Ajaz
 Nomenclature of Coordination
Compounds
• Nomenclature means naming of something
• Initially there were very few Coordination
complexes and names were given on the basis
of their colors or scientists or areas
• Later when the amount of complexes
increased, there was a need to give a
systematic names to the coordination
complexes/compounds
 IUPAC Nomenclature
• IUPAC gives a guideline for naming the
complexes in a systematic order as follows:
• A Metal complex can be a neutral entity or
exist in the form of a salt. In any case we
would at first look into how to name the
complex that is written in Parenthesis [ ]
[Ni(CO)4] (is a neutral complex)
K2[NiCl4] (is a complex salt)
• One should remember that anything within
parenthesis [] is a complex and is composed of
a metal atom/ion having covalently bonded to
the ligands. According to Werner the inner
circle of ligands is known as coordination
sphere
• Anything outside the parenthesis [] is having
an ionic interaction with the complex and is
only satisfying the charge over the complex
• Lets figure out how to name the complex part
that is expressed in parenthesis []
• A} Naming the complex given in parenthesis[]:
Order of naming inside complex:
1- Ligands
2- Metal
_______________________________________
1- Naming of Ligands:
Order of naming of Ligands:
According to their alphabetical order
Numerical value of monodentate ligands:
2(di), 3(tri), 4(tetra), 5(penta), 6(hexa)…..
Naming as per types of Ligands:
Ligands can be divided into three types:

i- Anionic
Will be negatively charged ligands and their
names will bear suffix –o instead of –ide
Cl- Chloride will become Chloro
Br- Bromide will become Bromo
CN- Cyanide will become Cyano
ii- Neutral
Generally the names of the neutral ligands will
bear no change with few exceptions:
H2O Water will be called Aqua or Aquo
CO Carbonmonooxide will be called Carbonyl
NH3 Ammonia will be called Ammine

iii- Cationic
They are very few and generally not discussed
but if any, they bear suffix –ium
N2H4+ Hydrazine will become hydrazinium
_______________________________________
2- Naming of Metals:
No change in the name of metal if the overall
complex is neutral of cationic.
BUT
If the complex is anionic overall, the name would
get a suffix –ate and the conventional names would
have to be used.
Fe would become Ferrate
Ag would become Argentate
Oxidation state of the metal must be specified in
Roman Numeric after the name of the metal in
brackets ()
If the complex is not a salt/compound or a netral
complex then it would be an ion itself. So the word
ion should be written at the end.

EXAMPLES OF WHAT WE HAVE LEARNT SO FAR:

[Fe (H2O)2Cl2Br2]- diaquodibromodichloroferrate(III)

ion
BUT HOW TO CALCULATE THE OXIDATION STATE OF
THE METAL?
[Fe (H2O)2Cl2Br2]-
REMEMBER!!! The charges over the ligands cant be
changed and are fixed. We have to see or calculate
the charge outside the complex and by subtracting
the charges of the ligands, we can calculate the
oxidation state of the metal.
Like in this example, charge at the complex is -1
Water is a neutral ligand with 0 formal charge
whereas -4 would be the charge coming from
anionic ligands. So metal must be having a +3
oxidation state to give a -1 formal charge outside
the complex
Lets see an example of a cationic complex:

[Co(NH3)4Cl2]+
tetraamminedichlorocobalt(III) ion

In this case, we have 2 chlorides giving -2 charge

and 4 ammonia ligands with 0 formal charge.
Therefore Cobalt must be in its +3 oxidation
state
Lets take example of a neutral complex:

[Ni(CO)4] Tetracarbonylnickel(0)

It should be noted that a neutral complex would

not bear “ion” at the end
• B} Naming what is outside the complex (if
written):

If the complex is not neutral then there might be

the counter ions given outside the complex to
make it a salt. In that case the ionic naming rule
will apply where cation is always names first
than anion. Like, Sodium Chloride, Potassium
Bromide. So, for example:
[Fe(NH3)4Br2]Cl
Tetraamminedibromoiron(III) Chloride
K2[AuCl4]2-
Potassium Tetrachloroaurrate(II)

Point to be noted that for the counterions (no

matter cations or anions) one does not require
to write any numerical values just like
NaCl would be Sodium Chloride
CaCl2 would be Calcium Chloride and not
Calcium di Chloride