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What is the 18-electron rule?

The 18-electron rule is a guideline in organometallic chemistry that helps predict the stability of transition metal complexes.

A transition metal complex tends to be most stable when the total number of electrons around the metal center (its own valence electrons + those donated by ligands) adds up to 18 electrons.

Why 18?

  • Transition metals have valence orbitals made up of:
    • 1 s orbital (can hold 2 electrons)
    • 3 p orbitals (can hold 6 electrons)
    • 5 d orbitals (can hold 10 electrons)
  • Together, these orbitals can hold 18 electrons maximum.
  • When the orbitals are filled (like in a noble gas configuration), the complex achieves extra stability.

Examples

  • Fe(CO)₅ (iron pentacarbonyl) → follows the 18-electron rule and is very stable.
  • Ni(CO)₄ → also follows the 18-electron rule.

Limitations

  • Not all complexes follow it strictly.
  • Complexes with bulky ligands, electron-poor metals, or metals in higher periods often deviate.
  • Still, it’s a useful rule of thumb for predicting stability in organometallics.

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