Coordination Complex

Typically consists of a complex ion and counterions (anions or cations as needed to

produce a neutral compound)

[Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]2+ and two Cl-; Co is in +3 oxidation state

K3[Fe(CN)6] [Fe(CN)6]3- and three K+; Fe is in +3 oxidation state

Coordination number is the Number of bonds formed between the metal ion and the
ligands in the complex ion. The most common coordination numbers are 4 and 6.

8
 Determine the primary and
secondary valencies and
propose the structures of
CoCl3.6NH3 , CoCl3.4NH3
and CoCl3.3NH3
Hint: [Co(NH3)6]Cl3
[Co(NH3)4(Cl)2]Cl
[Co(NH3)3(Cl)3]

Primary valency: ionizable (non-directional)

Secondary valency: nonionizable (coordination number, directional)

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The Metal Ion

3d

4d

5d

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 Ligands

Molecules that bind to metal with donor atoms having lone pair of electrons.
Types: Monodentate, polydentate, chelating ligands.
Dictate structures, chemical reactivity and photophysical properties.
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 Ligands

Neutral molecules or ions having a lone electron pair that can be used to form a bond to
a metal ion.

Monodentate ligand one bond to a metal ion

Bi and polydentate ligand Two or more bonds to a metal ion

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 EDTA - a Polydentate Ligand

EDTA4-

13
[Ca(EDTA)]2- Determine Primary/secondary valency? Shriver & Atkins 5e
 Coordination Numbers

Factors govern the coordination number:

1. Size of the central metal atom/ion.
2. Steric interactions between the ligands.
3. Electronic interactions between the central metal and the
ligands.
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Most Common Geometries of Coordination Complexes
[Ag(NH3)2]2+ [Pt(NH3)4]2+

C.N. = 2 C.N. = 4
[Co(NH3)6]3+
[Zn(NH3)4]2+

C.N. = 4 C.N. = 6 15
 Isomerism
On finding compounds with different properties follow the chart below

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 Ionization Isomerism
Interchange of an anionic ligand within the first coordination sphere with an anion outside the
coordination sphere.
[Cr(NH3)5(SO4)]Br and [Cr(NH3)5Br]SO4
[PtBr(NH3)3]NO2 and [Pt(NO2)(NH3)3]Br
Coordination Isomerism
Found in compounds in which both cations and anions are complex ions, arise from
interchange of ligands from the cationic part to the anionic part
[Co(NH3)6][Cr(C2O4)3] and [Cr(NH3)6][Co(C2O4)3]
[Zn(NH3)4][CuCl4] and [Cu(NH3)4][ZnCl4]
[PtII(NH3)4][PtIVCl6] and [PtIV(NH3)4Cl2][PtIICl4]

Hydrate Isomerism
Through interchange of water and another ligand between the first coordination sphere and the
outside ligands. [CrCl2(H2O)4]Cl.2H2O (bright-green)
[CrCl(H2O)5]Cl2.H2O (blue-green)
[Cr(H2O)6]Cl3 (violet) 17