Lecture on Metal Carbonyls

May 30, 2024

Lecture on Metal Carbonyls

Introduction

  • Discussing metal carbonyl compounds.
  • Formed by combination of transition metals with carbon monoxide (CO).
  • Types of metal carbonyls cover non-metallic carbonyls and those combining with vacant metals.

Metal Carbonyl Formation

  • Transition metals combine with CO to form strong bonds.
  • CO acts as a ligand and donates a pair of electrons to the metal.
  • Synergic bonding: CO accepts and donates electrons, forming strong bonds with metals.

Characteristics of CO as a Ligand

  • CO binds with transition metals forming coordinate bonds.
  • Acts as a Lewis base but can form strong bonds due to synergic bonding.
  • COтАЩs bonding is usually stable and hard to oxidize or dissociate.
  • CO can form terminal (one metal) or bridging bonds (between two metals).

Classification of Metal Carbonyls

  • Based on Ligands: Carbonyl Compounds: CO as ligand forming stable complexes.

On the Basis of the Number of Metals

  • Mononuclear: One metal atom in the complex.
  • Polynuclear: More than one metal atom; subdivided into homonuclear (same metal atoms) and heteronuclear (different metal atoms).
  • Terminal Ligands: Only bind to one metal atom.
  • Bridging Ligands: Bind to multiple metal atoms.
  • Examples: Fe3(CO)12 highlights three metal atoms with CO as ligand.

Reactions and Stability

  • Metal carbonyls typically do substitution reactions rather than oxidation.
  • Stability factors include metal-CO bond strength, bond order, and electron density.

Infrared Spectroscopy of Metal Carbonyls

  • Usage: Identifies metal carbonyl compounds even in crowded regions with other ligands.
  • CO Stretching Frequencies: Vary based on bond strength and electron density.
  • Higher electron density decreases stretching frequency of the CO bond.

Examples and Practical Analysis

  • CO stretching frequencies generally follow trends based on ligand types and metalтАЩs oxidation state.
  • Example: Nickel carbonyl complexes like Ni(CO)_4 differ in frequency based on ligand attachment.
  • Questions: Determine the highest CO stretching frequency based on formal charges and ligand types.

Molecular Orbital Theory (MOT) of CO

  • COтАЩs electron configuration and bonding explained through MOT.\n- Anti-bonding and bonding orbitals play a crucial role in understanding the stability and reactivity of the CO-formed bonds.
  • Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of CO discussed for interaction with transition metals.

Metal Carbonyl Bridging and Terminal Bonding

  • Structural differences between bridging and terminal CO bonds.
  • Impact of metalтАЩs oxidation state on the CO bonding.
  • Example: CO bonding in Fe_3(CO)_12 firm due to bridging and terminal explanations.

Factors Affecting Metal CarbonylsтАЩ Stability

  • Electron density, oxidation state, and ligand types crucial for stability.
  • Infrared spectroscopic data aligns with bonding models and theoretical predictions.

Organometallic Chemistry Aspects

  • Transition metals and CO forming various organometallic compounds.
  • Application of molecular orbital theory and synergistic bonding in organometallic complexes.

Conclusion

  • CO binds strongly with transition metals due to synergistic behavior.
  • Metal carbonyl complexes exhibit distinct properties that align with spectroscopic and theoretical analyses.
  • Practical applications and examples reinforce concepts of metal carbonyl chemistry.