Periodic Chemistry

Coordination Complex

Metal ions surrounded by ligands — colorful chemistry of transition metals

A coordination complex is a structure with a central metal ion bonded to surrounding ligands (Lewis bases). Bonds are coordinate covalent (both electrons from ligand). Common ligands: H₂O, NH₃, Cl⁻, CN⁻, EDTA. Coordination number: number of ligand bonds (typically 4 or 6). Geometries: tetrahedral, square planar, octahedral. Properties: distinctive colors (d-d transitions), magnetism (high vs low spin), bioactivity. Examples: hemoglobin (Fe-based), chlorophyll (Mg-based), vitamin B12 (Co-based), platinum drugs (Pt-based — cisplatin).

  • ComponentsCentral metal + ligands
  • BondCoordinate covalent (Lewis acid-base)
  • Coordination numbers4 or 6 most common; 2-12 possible
  • GeometriesTetrahedral, square planar, octahedral
  • Examples[Cu(H₂O)₆]²⁺, hemoglobin, [PtCl₂(NH₃)₂] (cisplatin)
  • PropertiesColor, magnetism, catalysis, biological function

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Why coordination complexes matter

  • Biology. Hemoglobin, chlorophyll, B12.
  • Drugs. Cisplatin, MRI contrast agents.
  • Catalysis. Many industrial catalysts.
  • Color. Pigments, dyes, gem stones.
  • Analytical. Detection of metals.
  • Materials. Coordination polymers, MOFs.
  • Environmental. Heavy metal remediation via chelation.

Common misconceptions

  • All metals form complexes. Specific transition metals; alkali less.
  • Coordination = ionic. Coordinate covalent.
  • Color from metal alone. Ligand affects via splitting.
  • Geometry is fixed. Multiple possible per coordination number.
  • Cis-trans not important. Critical (cisplatin example).
  • Chelation just stronger. Specifically multidentate; entropy effect.

Frequently asked questions

What's a coordination complex?

Central metal ion + surrounding ligands. Ligands donate lone pair to metal — coordinate covalent bond. Metal acts as Lewis acid; ligands as Lewis bases. Typical: transition metals (have d-orbitals to accept electrons). Counter-ions balance charge if any. [Cu(H₂O)₆]²⁺ written: 6 water ligands around Cu²⁺.

What are common ligands?

Many. Monodentate (1 bond): H₂O, NH₃, Cl⁻, CN⁻, OH⁻, CO. Bidentate (2 bonds): ethylenediamine (en), glycinate. Polydentate: EDTA (4-6 bonds). Heme (4 N donors). Crown ethers. Specifically: nitrogen, oxygen, sulfur most common donor atoms. Strong ligands: CN⁻, CO. Weak: H₂O, halides.

Why are they colored?

d-d transitions. Ligands split d orbitals (Crystal Field Theory). Energy gap matches visible light. Absorption of certain wavelengths → complementary color seen. Examples: [Cu(H₂O)₆]²⁺ blue (absorbs orange). [Cu(NH₃)₄]²⁺ deep blue (absorbs orange-yellow more). Different ligands → different splittings → different colors.

What's Crystal Field Theory?

Approach to bonding in complexes. Ligands generate electric field; splits 5 d-orbitals into different energies. Octahedral: 3 lower (t₂g) + 2 higher (eg). Energy gap Δ depends on: metal, ligand, geometry. Stronger ligand field: larger Δ. Spectrochemical series: I⁻ < Br⁻ < Cl⁻ < F⁻ < H₂O < NH₃ < CN⁻ < CO. Predicts: color, magnetism.

What's hemoglobin?

Iron-based coordination complex. Heme group: porphyrin (4 N donors) + Fe²⁺ + 5th ligand (proximal histidine of protein) + 6th ligand (O₂ or CO). Reversible O₂ binding for transport. CO binds 200× stronger than O₂ — toxic (poisoning). Each hemoglobin: 4 heme units; cooperative binding makes O₂ uptake/release efficient.

What's cisplatin?

Platinum-based anticancer drug. [Pt(NH₃)₂Cl₂] — square planar geometry. Cl⁻ ligands replaced by water; binds DNA; prevents replication. Transplatin (trans isomer): doesn't work. Cis-trans isomerism critical. One of most successful chemotherapy drugs (testicular cancer cure rate >95%). Side effects significant; newer Pt drugs: carboplatin, oxaliplatin.

What's chelation?

Multidentate ligand wraps around metal — forms ring. Stronger bond than separate ligands. Examples: EDTA — 6 donors; binds metals tightly. Used: heavy metal poisoning (Pb, Hg, Cd) treatment, water softening (binds Ca, Mg), analytical chemistry (titrating metals). Chelate effect: entropy favors fewer particles (6 H₂O released for 1 EDTA bound).