IB Chemistry R3.4 R3.4.8
R3.4.8 HL

Complex Ions and Ligands

Key Definitions

  • Complex ion: A charged species consisting of a central metal cation bonded to surrounding molecules or anions (ligands) via coordination bonds.
  • Ligand: A molecule or anion that donates a lone pair to the central metal ion, acting as a Lewis base.
  • Coordination number: The total number of coordination bonds formed between the ligands and the central metal ion.

How Complex Ions Form

Transition metal cations have empty d orbitals that can accept lone pairs from ligands. Each ligand acts as a Lewis base and donates an electron pair to the metal ion (Lewis acid), forming a coordination bond.

Writing Complex Ion Formulas

Complex ion formulas are written in square brackets [ ] with the overall charge as a superscript outside. The metal ion is written first, followed by the ligands.

Common Ligands

Ligand Formula Charge Lone pairs donated
WaterH₂O01 (from O)
AmmoniaNH₃01 (from N)
ChlorideCl⁻-11 (from Cl)
CyanideCN⁻-11 (from C)

Deducing the Charge on a Complex Ion

This is a key exam skill. The overall charge is calculated as:

Charge Formula

Overall charge = (charge on metal ion) + (sum of charges on all ligands)

Neutral ligands (H₂O, NH₃) contribute 0. Charged ligands (Cl⁻, CN⁻) contribute their charge.

Worked Examples

Complex ion Metal charge Ligand charges Overall charge Coord. no.
[Cu(H₂O)₆]²⁺Cu²⁺ = +26 x 0 = 0+26
[Fe(CN)₆]³⁻Fe³⁺ = +36 x (-1) = -6-36
[CuCl₄]²⁻Cu²⁺ = +24 x (-1) = -4-24
[Ag(NH₃)₂]⁺Ag⁺ = +12 x 0 = 0+12

Coordination Number and Geometry

Coordination number Common geometry Example
6Octahedral[Cu(H₂O)₆]²⁺
4Tetrahedral or square planar[CuCl₄]²⁻ (tetrahedral)
2Linear[Ag(NH₃)₂]⁺

Think About It

Given the formula [Co(NH₃)₆]Cl₃, what is the charge on the complex ion and the oxidation state of cobalt?

There are 3 Cl⁻ ions outside the brackets, so the complex ion [Co(NH₃)₆] must have a charge of +3 to balance. Since NH₃ is neutral, cobalt must be Co³⁺ (oxidation state +3).

Common Exam Mistakes

  • Forgetting that neutral ligands (H₂O, NH₃) do not contribute to the overall charge.
  • Confusing coordination number with oxidation state. Coordination number = number of bonds to the metal.
  • Not writing the complex ion in square brackets with the charge outside.
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← R3.4.7 Coordination BondsR3.4.9 SN1/SN2 Mechanisms →