key term - Back-bonding

Definition

Back-bonding is a type of coordination bonding where electrons are donated from a filled orbital of a metal to an empty orbital of a ligand, typically a π-acceptor. This process enhances the stability of the complex and plays a significant role in the properties and reactivity of organometallic compounds, allowing for unique interactions between metals and ligands. It is particularly important in understanding how metal-ligand interactions contribute to the overall electronic structure and reactivity in these compounds.

5 Must Know Facts For Your Next Test

1. Back-bonding is crucial for stabilizing organometallic complexes by lowering their energy and enhancing their reactivity.
2. Common examples of ligands that participate in back-bonding include carbon monoxide (CO) and certain alkenes, which have π-acceptor characteristics.
3. The effectiveness of back-bonding depends on the metal's oxidation state and electronic configuration, as well as the nature of the ligand.
4. In back-bonding, the energy levels of the filled metal d-orbitals and the empty ligand orbitals need to be compatible for effective overlap.
5. This type of bonding can influence molecular properties such as bond lengths and vibrational frequencies in organometallic compounds.

Review Questions

• How does back-bonding influence the stability and reactivity of organometallic compounds?
  • Back-bonding enhances the stability of organometallic compounds by allowing for effective overlap between filled metal d-orbitals and empty π* orbitals of ligands. This interaction stabilizes the overall complex by lowering its energy. Additionally, back-bonding can also affect reactivity by altering the electronic environment around the metal center, making it more or less reactive depending on the nature of the ligand involved.
• What role do π-acceptor ligands play in the mechanism of back-bonding and how does it compare with σ-donation?
  • π-acceptor ligands are crucial for back-bonding because they possess empty π* orbitals that can accept electron density from filled metal d-orbitals. This is different from σ-donation, where ligands provide electron pairs to form sigma bonds. In many cases, both processes occur simultaneously in organometallic complexes, where σ-donation provides initial stabilization while back-bonding further enhances it by increasing electron density at the metal.
• Evaluate how variations in oxidation states of metals influence back-bonding capabilities and provide an example.
  • The oxidation state of a metal significantly affects its back-bonding capabilities because it determines the electron count and distribution around the metal center. For example, a low oxidation state metal may have more d-electrons available for back-bonding compared to a high oxidation state counterpart, which may have fewer available electrons. This can lead to differences in ligand preferences; for instance, nickel in a +2 oxidation state often forms stable complexes with CO due to effective back-bonding, while nickel in a higher oxidation state may prefer different ligands that do not rely on this interaction as heavily.

Related terms

π-acceptor ligands: Ligands that can accept electron density from metal d-orbitals through their empty π* orbitals, facilitating back-bonding.

σ-donation:

The process where a ligand donates a pair of electrons to an empty orbital on the metal, forming a sigma bond; this often works alongside back-bonding.

metal-ligand complex: A structure formed when a metal ion is coordinated to one or more ligands, which can involve various types of bonding, including back-bonding.