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Organometallic Ligands: Carbonyls, Phosphines and Hapticity

The ligands of organometallic chemistry are chosen for what they do to the metal, not just for binding. Carbon monoxide reports on electron density through its stretching frequency, phosphines are tuned by their substituents, and carbon chains can bind through several atoms at once.

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What a learner can do afterwards

  • Explains back-donation into the carbonyl antibonding orbital and predicts the effect on its stretching frequency
  • Uses a measured carbonyl frequency to compare electron density at two metal centres
  • Assigns hapticity for alkene, allyl and cyclopentadienyl ligands and counts their electron contribution
  • Explains how changing a phosphine's substituents changes both its donor strength and its size

1 · Read

A coordination compound is a team: a metal centre plus ligands, where each ligand lends the metal an electron pair in a coordinate bond. A monodentate ligand holds on with one donor atom, like water through its oxygen. A polydentate ligand wraps round with several donor atoms, forming a chelate that grips like a claw.

Carbon monoxide does more than just bind. It donates sigma density to the metal and then accepts metal density back into its empty pi orbitals. That return gift weakens the CO bond itself, so the stretching frequency drops. The richer the metal centre, the more back donation and the lower the frequency: compare a neutral carbonyl with its anion and the anion absorbs lower.

Try it together

Carbon chains can bind through several neighbouring atoms at once, and the Greek prefix names the touch count: that is hapticity. An alkene touches through two atoms, an allyl through three, and a cyclopentadienyl ring through five. Count the touching atoms to tally the electrons the ligand contributes.

Good to know

Phosphines are the tunable ligands of the set. Changing their substituents shifts both their donor strength and their bulk at the metal. So when comparing two centres, read the carbonyl frequency for electron richness and check the phosphine substituents for donor power and size.

CO reports richness through its frequency, hapticity counts touching atoms, and phosphines tune donation and bulk.

2 · Watch

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Organometallic Ligands: Carbonyls, Phosphines and Hapticity · Science, ages 20 to 21 · LightMySky