CHAPTER 2

NOMENCLATURE OF
COORDINATION
COMPOUNDS
 Important Rules
1. The cation is written before the
anion.

2. The charge of cation is balanced

by the charge of anion.

3. In the complex ion, neutral ligand

are written before anionic ligand
and the formula for the whole ion
is placed in brackets.
 Nomenclature Rules
1. Cation is named first before anion.

 [Co(NH3)4Cl2]Cl

[Co(NH3)4Cl2] + Cl-
Name: tetraamminedichlorocobalt(III) chloride

2. Within the coordination sphere, the ligands are named before the metal, but in the structure formulas the metal ion is written first.

 [Co(NH3)4Cl2]Cl

tetraamminedichlorocobalt(III) chloride
  [Co(NH3)5SO4]NO2

pentaamminesulfatocobalt(III) nitrite

 Na3[FeCl(CN)5]

sodium chloropentacyanoferrate(III)

3. Ligands are named in alphabetical order (according

the name of the ligand, not the prefix).

 [Co(NH3)4Cl2]Cl

tetraamminedichlorocobalt(III) chloride

 [CoBr(NH3)5]SO4

pentaamminebromocobalt(III) sulfate
4. A numerical prefix indicates the number of
ligands of a particular type. These prefix do not
affect the alphabetical order. If the ligand name
includes these prefixes or is complicated, use the
second set of prefix.

1st set 2nd set

2 di bis
3 tri tris
4 tetra tetrakis
5 penta pentakis
6 hexa hexakis
7 hepta heptakis
8 octa octakis
9 nona nonakis
10>>>
deca decakis
 [Co(NH3)4Cl2]Cl
tetraamminedichlorocobalt(III) chloride

 [Fe(NH4C5-C5H4N)3]2+

bipyridine

tris(bipyridine)iron(II) ion

 [Co(en)3Cl3]

trichlorotris(ethylenediammine)cobalt(III)

• [Co(C5H5N)4(As(C6H5)3)2]Cl3

tetrakis(pyridine)bis(triphenylarsine)cobalt(III) chloride
5. For anionic ligands(-Ve ion) generally end the name with –o after the root name.
 Anion (-ide is replaced with –o)
 F- fluoride  fluoro
 Cl- chloride  chloro
 CN- cynide  cyano
 Br- bromide  bromo
 O2- oxide  oxo
 O22- peroxide  peroxo
 O2- superoxide  superoxo
 OH- hydroxide  hydroxo
 N 3- azide  azido
 N3- nitride  nitrido
 NH2- amide  amido
 S2- sulfide  sulfido
 [CH3O]- methoxide  methoxo
 Anion (-ate is replaced with –o)
CO3 2- carbonate  carbonato
CNO cynate  cynato
NO3- nitrate  nitrato
C2O42- oxalate  oxalato
CH3COO- acetate  acetato

NO3- nitrate  O-nitrato (O-bonded)

NO3- nitrate  N-nitrato (N-

bonded)
SCN- thiocyanate  S-thiocyanato (S-
bonded)
NCS- thiocyanate  N-thiocyanato (N-
bonded)
SO 2- sulfate  sulfato
 Anion (-ite is replaced with –ito)

NO2- nitrite  nitrito

SO3- sulfite  sulfito

 Miscellaneous anions
H-  hydrido /
hydro
N3-  azido
N3-  nitrido
[NH2]-  amido
C6H5-  phenyl (ph)
C5H5-  cyclopentadienyl
Examples:

K3[CoF6]
potassium hexaflourocobaltate(III)

[Co(SO4)(NH3)5]+
pentaamminesulfatocobalt(III) ion

Na2[NiCl4]
Sodium tetrachloronickelate(II)
6. For neutral ligand their names are not changed, except the
following few:
H 2O water  aqua
NH3 ammonia  ammine
CO carbon monoxide  carbonyl
NO nitrogen monoxide  nitrosyl
O2 oxygen  dioxygen
N2 nitrogen  dinitrogen
C 5 H5N pyridine  (py)
H2NCH2CH2NH2 ethylenediamine  (en)
1,10-phenanthroline  (phen)
2,2’-bipyridine  (bipy)
Triphenylphosphine P(C6H5)3  (PPh3)
H2NCH2CH2NHCH2CH2NH2 diethylenetriamine  (dien)
O O

C C acetylacetonato  (acac)
H3C C CH3
H

NH2CH2COO- glycinato  (gly)

(OOCCH2)NCH2CH2N(CH2COO)24-
ethylenediaminetetraacetato  (EDTA)

O O
C2O42- C C

O O
oxalato  (ox)
7. A roman numeral or a zero in parentheses is used
to indicate the oxidation state of the central metal
atom
• [Co(NH3)4Cl2]Cl :

Co3+

tetraamminedichlorocobalt(III) chloride

• (NH4)2[CuCl4] :

Cu2+

ammonium tetrachlorocuprate(II)
8. For a neutral and cation complexes (+Ve) the metal
name is unchange. But for anion complexes (-Ve),
drop the ending of the metal name and add –ate
• cation complexes

[Co(NH3)4Cl2]Cl

Name: tetraamminedichlorocobalt(III) chloride

• neutral complexes

[Cu(NH3)2Cl2]

Name: diamminedichlorocopper(II)

• anion complexes

Na[B(NO3)4]

Name: sodium tetranitratoborate(III)

9. The prefixes cis- and trans- designate adjacent and
opposite geometric locations. Other prefixes are used as
well and will de introduced as needed in the text.

H3N Cl
Pt
H3N Cl

cis -diamminedichloroplatinum(II)
• [PtCl2(NH3)2]

H3N Cl

Pt
Cl H3N

trans-diamminedichloroplatinum(II)
10. Bridging ligands between two metal ions have the prefix µ-.
A bridging ligands is indicated by placing a µ- before its name.
The µ- should be repeated for every bridging ligands.

• (H3N)3Co(OH)3Co(NH3)3

hydroxo
3+
H
O
(NH3)3 Co H Co (NH3)3
O
O
H

• Name: triamminecobalt(III)-µ-trihydroxotriamminecobalt(III)
 O22- = peroxo

 [(NH3)5Co O-O Co(NH3)5]4+

0 + Co + (-2) + Co = +4
2Co = +6 Co = +3

Pentaamminecobalt(III)-µ-peroxopentaamminecobalt(III)
OR
µ-peroxo-bis[pentaamminecobalt(III)]
 O2 O2- = superoxo
4+
(NH3)4Co Co(NH3)4
N
H2

0 + Co + (-1) + (-1) + Co + 0 = +4
Co = +3

Tetraamminecobalt(III)-µ-amido-µ-superoxotetraammine
cobalt(III)
OR

µ-amido-µ-superoxobis[tetraamminecobalt(III)]
 Example in naming
coordination compound:
 Na3[AlF6]
Central metal
Al: x + 6(-1) = -3
Al = +3
[AlF6]3- Al3+  aluminate(III)
ligands
six F- (fluoro)  hexafluoro
-Ve complex

Name: sodium hexafluoroaluminate(III)

 Central metal :Cu2+  Copper(II)

 [Cu(NH3)2Cl2] Ligands:
Two NH3 (diammine)
Two Cl- (dichloro)

Neutral compound

Name: diamminedichlorocopper(II)
 [Cu(NH3)4]SO4

Cu2+ Copper (II)

Cu(NH3)42+

Four NH3 tetraammine

+Ve complex

Name: tetraamminecopper(II) sulfate

 [CuCl4]2-
Cu2+ Cuprate (II)

-Ve complex Four Cl tetrachloro

Name: tetrachlorocuprate(II) ion

 [Cr(en)3](NO3)3

Cr3+ Chromium (III)

[Cr(en)3]3+

Three en Tris(etylenediamine)
+Ve complex

Name: Tris(etylenediamine)chromium(III) nitrate

 Tetraamminecopper(II) sulfate

ligand Central Counter ion

metal

(NH3)4 Cu2+ SO42-

[Cu(NH3)4] + SO42-
+2 + 0 = +2

[Cu(NH3)4] SO4
 Potassium diamminetetrabromocobaltate(III)

K+ [Co (NH3)2Br4] -
+3 + 4(-1) + 2(0) = -1

K [Co (NH3)2Br4]
 Ammonium tetrachlorocuprate(II)

NH4+ [CuCl4] 2-
+2 + 4(-1) = -2

(NH4)2 [CuCl4]