Complex Ions, Ligands and Colour
A complex ion is a central metal ion with ligands bonded by dative (coordinate) bonds. Coordination number = number of dative bonds: 6 → octahedral ([Cu(H₂O)₆]²⁺); 4 → tetrahedral ([CuCl₄]²⁻, with large Cl⁻) or square planar (cisplatin, Pt); 2 → linear ([Ag(NH₃)₂]⁺). Ligands may be monodentate (H₂O, NH₃, Cl⁻), bidentate (en, C₂O₄²⁻) or polydentate (EDTA⁴⁻, 6 bonds). Colour: ligands split the d orbitals; an electron absorbs visible light of energy to jump up; the complementary colour is seen. Changing ligand, coordination number or oxidation state changes ΔE and so the colour. Ligand exchange is favoured by larger and by the chelate effect (entropy increase). Complexes show cis/trans and optical isomerism.
Learning objectives
- Define ligand, complex and coordination number.
- Predict shapes of complexes.
- Explain colour using d-orbital splitting.
- Describe ligand exchange, stability constants and stereoisomerism.
Copper sulfate solution is blue, but anhydrous copper sulfate is white. Why?
Core idea
The same copper ion can be pale blue in water, yellow-green in concentrated HCl and deep blue in ammonia. Only the ligands change.
Ligands donate lone pairs to a central ion and split its d orbitals. The size of the split decides which light is absorbed, and so the colour we see.
1. Shapes
Count dative bonds, not ligands.
2. Colour
- Ligand lone pairs repel some d orbitals more than others.
- An electron absorbs a photon of matching energy and moves up.
- ΔE for water ligands matches roughly 800 nm.
- We see the complementary colour.
Why is so favourable?
- Goal
- Explain using ΔS.
- Strategy
- Count particles.
- More particles on the right.
- Similar Cu–N and Cu–O bond strengths.
Summary
- Dative bonds from ligands.
- Shapes from coordination number.
- Colour: complementary to absorbed light.
- Chelate effect; cis/trans and optical isomers.
- Ligand
- Species donating a lone pair to a central metal ion.
- Bidentate
- Ligand forming two dative bonds.
- Chelate effect
- Multidentate ligands replace monodentate ones due to entropy increase.
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