In the earlier days, the compounds were named after their discoverers. For example,K[Ptcl3(c2H4)] was called Zeise’s salt and [Pt(NH3)4][Ptcl4] is called Magnus’s green salt etc… There are numerous coordination compounds that have been synthesised and characterised. The International Union of Pure and Applied Chemistry (IUPAC) has developed an elaborate system of nomenclature to name them systematically. The guidelines for naming coordination compounds based on IUPAC recommendations (2005) are as follows:

  1. The cation is named first, followed by the anion regardless of whether the ion is simple or complex. For example

• In k4[Fe(CN)6], the cation k+ is named first followed by[Fe(CN)6]4-.

• In [Co(NH3)6]cl3, the complex cation [Co(NH3)6] 3+ is named first followed by the anion Cl-

• In [Pt(NH3)4][Ptcl4], the complex cation [Pt(NH3)4] 2+is named first followed by the complex anion [Ptcl4]2-

  1. The simple ions are named as in other ionic compounds. For example,
Simple cation Symbol Simple anion Symbol
Sodium Na+ Chloride Cl-
Potassium k+ Nitrate No3-
Copper Cu2+ Sulphate So42-
  1. To name a complex ion, the ligands are named first followed by the central metal atom/ion. When a complex ion contains more than one kind of ligands they are named in alphabetical order.

    a. Naming the ligands:

    i. The name of anionic ligands ends with the letter ‘o’ and the cationic ligand ends with ‘ium’. The neutral ligands are usually called with their molecular names with fewer exceptions namely, H2O (aqua), CO (carbonyl), NH3 (ammine) and NO (nitrosyl).

    ii. A κ-term is used to denote an ambidendate ligand in which more than one coordination mode is possible. For example, the ligand thiocyanate can bind to the central atom/ ion, through either the sulfur or the nitrogen atom. In this ligand, if sulphur forms a coordination bond with metal then the ligand is named thiocyanato-κS and if nitrogen is involved, then it is named thiocyanato-κN.

C ommon name Formula IUPAC ligand name
Bromide Br- bromido
Chloride Cl- chlorido
Fluoride F- uorido
Cyanide CN- cyanido
Hydroxide OH- hydroxido
Carbonate Co23- carbonato
Nitrate No3- nitrato
Nitrite No2- ←NO- ; nitrito-κN ←ONO- ; nitrito-κo2
Sulphate So24- sulphato
Sulphide S2- sulphido
Oxalate (ox) C2o42- oxalato
Ethylenediamine (en) H NNH22 ethane-1,2-diamine
Ethylenediaminetetraacetate (EDTA) O-O O-O NN O-O O-O 2,2’,2’’,2’’’-(ethane-12-diyldinitrilo
tetraacetato
Triphenylphosphine P(Ph)3 triphenylphosphane
Pyridine (py) N pyridine

iii. If the coordination entity contains more than one ligand of a particular type, the multiples of ligand (2, 3, 4 etc…) is indicated by adding appropriate Greek prefixes (di, tri, tetra, etc…) to the name of the ligand. If the name of a ligand itself contains a Greek prefix (eg. ethylenediamine), use an alternate prefixes (bis, tris, tetrakis etc..) to specify the multiples of such ligands. These numerical prefixes are not taken into account for alphabetising the name of ligands.

b. Naming the central metal: In cationic/neutral complexes, the element name is used as such for naming the central metal atom/ion, whereas, a suffix ‘ate’ is used along with the element name in anionic complexes. The oxidation state of the metal is written immediately after the metal name using roman numerals in parenthesis.

Element Name of the metal in

Element Name of the metal in
cationic complex anionic complex
Cr Chromium Chromate
Zn Zinc Zincate
Al Aluminum Aluminate
Fe Iron Ferrate
Cu Copper Cuprate
Co Cobalt Cobaltate
Pb Lead Plumbate
Ag Silver Argentate
Sn Tin Stannate
Au Gold Aurate
Pt Platinum Platinate

Example 1:

C oordination C ompound : K4[Fe(CN)]6
Cation (Simple) k+ Potassium
Anion (complex) [Fe(CN)6]4-
Ligands CN-
Name of the ligand with prex 6 ligands - prex: hexa Anionic ligand: cyanido-κC - (Coordinating atom in CN is carbon) hexacyanido-κC
Central metal Fe (in anionic complex) ferrate
Oxidation state of central metal (x) x + 6 (-1)= -4x = -4 + 6 = +2 (II)
IUPAC Name: Potassium hexacyanido-κC ferrate(II)

Example 2: Coordination Compound : [Co(NH3)4cl2]Cl

Example 2: C oordination C ompound : [Co(NH ) Cl ]cl3 4 2
Cation (complex) [Co(NH ) Cl ]+3 4 2
ligands -NH and cl3
Name of the ligand (NH ) with prex3 4 ligands - prex: tetraNeutral ligand: ammine tetraamminedichlorido(alphabatically ammine comes before chlorido)
2 ligands - prex: diAnionic ligand: chlorido
Central metal Co (in cationic complex) cobalt
Oxidation state of central metal (x) x + 4 (0) + 2 (-1)= +1x = 1 + 2 = +3 (III)
Anion (simple) -Cl chloride
IUPAC Name: Tetraamminedichloridocobalt(III) chloride

Example 3:. Coordination Compound : [Cr(en)3][CrF6]

Example 3:. C oordination C ompound : [Cr(en) ][CrF ]3 6
Cation (complex) [Cr(en) ]3+3
ligands en - (ethylenediamine)
Name of the ligand with prex(Ligand itself contains a Greek prex - di, use alternate prex) 3 ligands - prex: trisNeutral ligand: ethane-1,2-diamine tris(ethane-1,2-diamine)
central metal Cr (in cationic complex) chromium
Oxidation state of central metal (x) x + 3 (0) = +3x = +3 (III)
Anion (Complex) 3-[CrF ]6
ligands -6 F
Name of the ligand with prex 6 ligands - prex: hexaAnionic ligand: Fluorido hexauorido
central metal Cr (in anionic complex) chromate
Oxidation state of central metal (x) x + 6 (-1)= – 3x = -3 + 6 = +3 (III)
IUPAC Name: Tris(ethane-1,2-diamine)chromium(III) hexauoridochromate(III)

More examples with names are given in the list below for better understanding of IUPAC Nomenclature:

i. [Ag((NH)3)2]Cl Diamminesilver(I) chloride
ii. [Co(en)2 Cl2 ]cl Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride
iii. [Cu(NH)]So3 4 4 Tetraamminecopper(II) sulphate
iv. [Co(CO )(NH ) ]cl3 3 4 Tetraamminecarbonatocobalt(III) chloride
v. [Cr(NH ) (H O) ]cl3 3 2 3 3 Triamminetriaquachromium(III) chloride
vi. K [Fe(CN) NO]3 5 Potassiumpentacyanidonitrosylferrate(II)
vii. Na [Ni(EDTA)]2 Sodium 2,2’,2’’,2’’’-(ethane-1,2-diyldinitrilo)tetraacetatonickelate(II)
viii. [PdI (ONO) (H O) ]2 2 2 2 Diaquadiiododinitrito-κO palladium(IV)
ix. [Cr(PPh )(CO) ]3 5 Pentacarbonyltriphenylphosphanechromium(0)
x. [Co(NO ) (NH ) ]2 3 3 3 Triamminetrinirito-κNcobalt(III)
xi. [Co(NH ) CN][Co(NH )(CN) ]3 5 3 5 Pentaamminecyanido-κCcobalt(III) amminepentacyanido-κCcobaltate(III)
xii. [Pt(py) ][PtCl ]4 4 Tetrapyridineplatinum(II) tetrachloridoplatinate(II)
xiii. [Co(NH ) Cl ] [Cr(CN) ]3 4 2 3 6 Tetraamminedichloridocobalt(III) hexacyanido-κCchromate(III)
xiv. [Ag(NH ) ]+3 2 diamminesilver(I) ion
xv. [Co(NH ) Cl]2+3 5 pentaamminechloridocobalt(III) ion
xvi. [FeF ]4-6 Hexauoridoferrate(II)ion

Evaluate yourself 3:

a. Write the IUPAC name for the following compounds.

(i) K2[Fe(CN)3(Cl)2(NH)3]

(ii) [Cr(CN)2 (H2 O )4]

(iii) [Cu(NH3)2 cl2]

(iv) [Cr(NH3)3(Nc)2(H2O)]+

(v) [Fe(CN)6]4-

b. Give the structure for the following compounds.

(i) diamminesilver(I) dicyanidoargentate(I)

(ii) Pentaammine nitrito-κNcobalt (III) ion

(iii) hexafluorido cobaltate (III) ion

(iv) dichloridobis(ethylenediamine) Cobalt (IV) sulphate

(v) Tetracarbonylnickel (0)


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