What is the Difference Between Inner and Outer Sphere Mechanism

Inner and outer sphere mechanisms are two ways electron transfer can occur in chemistry, particularly involving transition metal complexes. Both mechanisms involve metal complexes as the electron donor and acceptor species.

What is the difference between inner and outer sphere mechanism? The inner sphere mechanism involves a bridging ligand, whereas the outer sphere mechanism does not involve a bridging ligand.

Key Areas Covered

1. What is the Inner Sphere Mechanism
      – Definition, Features
2. What is the Outer Sphere Mechanism
      – Definition, Features 
3. Similarities Between Inner and Outer Sphere Mechanism
      – Outline of Common Features
4. Difference Between Inner and Outer Sphere Mechanism
      – Comparison of Key Differences
5. FAQ: Inner and Outer Sphere Mechanism
      – Answers to Frequently Asked Questions

Key Terms

Inner Sphere Mechanism, Outer Sphere Mechanism

Difference Between Inner and Outer Sphere Mechanism - Comparison Summary

What is the Inner Sphere Mechanism

The inner sphere mechanism refers to a specific pathway for electron transfer between molecules, especially involving metal complexes. A crucial element in this mechanism is a bridging ligand. This molecule acts as a physical connection between the two reacting metal centers. The ligand needs to be able to bond with both metals simultaneously. Common bridging ligands include halides (like chloride) and pseudohalides (like hydroxide). The bridging ligand in the inner sphere mechanism facilitates a closer interaction between the metals.

The electron transfer can occur in a couple of ways. The electron might directly jump from the donor metal to the acceptor metal through the bridge. The electron might also first move to the bridging ligand and then get transferred to the acceptor metal. The inner sphere mechanism can be faster than the outer sphere mechanism due to the more intimate interaction between the reactants. It allows for coupled electron transfer and atom transfer (bond breaking/formation), which is needed in reactions like photosynthesis.

Inner and Outer Sphere Mechanism

What is the Outer Sphere Mechanism

The outer sphere mechanism is another way electron transfer occurs in chemistry, especially between metal complexes. Unlike the inner sphere mechanism, there’s no bridging ligand involved in the outer sphere mechanism. The electron transfer happens directly between the metal centers of the reactants, with the solvent molecules separating them.

A key feature of the outer sphere mechanism is that no bonds are broken or formed during the electron transfer itself. The reacting molecules maintain their original structures throughout the process. This makes it a simpler and potentially faster mechanism compared to the inner sphere mechanism. Due to the simpler interaction and lack of bond rearrangements, the outer sphere mechanism is often faster than the inner sphere mechanism. This is because less energy is required for the electron transfer to occur.

Similarities Between Inner and Outer Sphere Mechanism

  1. Both mechanisms aim to achieve the same outcome – the transfer of an electron from a donor molecule to an acceptor molecule.
  2. Both mechanisms involve metal complexes as the electron donor and acceptor species.
  3. These mechanisms maintain the overall electrical neutrality of the system.

Difference Between Inner and Outer Sphere Mechanism

Definition

  • The inner sphere mechanism refers to a specific pathway for electron transfer between molecules, especially involving metal complexes. However, the outer sphere mechanism refers to a pathway for electron transfer between molecules, where the electron transfer occurs without direct bonding or significant interaction between the inner coordination spheres of the involved metal complexes.

Bridging Ligand

  • The inner sphere requires a bridging ligand that bonds to both the electron donor and acceptor metals, creating a physical connection. However, the outer sphere does not involve a bridging ligand. The electron transfer occurs directly between the metal centers separated by solvent molecules.

Bond Breaking and Forming

  • In the inner sphere, bond breaking and formation can occur during the electron transfer process as the metals come closer and interact with the bridging ligand. However, in the outer sphere, no bonds are broken or formed during the electron transfer itself. The reacting molecules maintain their original structures.

Rate

  • The inner sphere can be slower than the outer sphere mechanism due to the more complex interaction involving bond changes.

Conclusion

Inner and outer sphere mechanisms are two pathways for electron transfer in chemistry, especially for transition metal complexes. The main difference between inner and outer sphere mechanism is the presence of a bridging ligand. Inner sphere uses a bridge to connect the metals, allowing for faster transfer and coupled atom transfer. Outer sphere has no bridge, keeps the original structures of reactants, and can be simpler and potentially faster.

FAQ: Inner and Outer Sphere Mechanism

1. What is the inner sphere mechanism with an example?

The inner sphere transfers electrons via a bridging ligand. For example, iron (Fe) loses an electron to chlorine (Cl). Fe-Cl bridges them, Cl gets the electron, and Fe-Cl breaks apart.

2. What are the two types of coordination spheres?

There are two main types of coordination spheres, as inner sphere and outer sphere. Inner sphere is also called as first coordination sphere or primary sphere while outer sphere is called as secondary sphere or second coordination sphere.

3. What is the inner and outer coordination sphere?

The terms inner and outer coordination sphere refer to specific regions around a central metal atom in coordination chemistry. The inner sphere is the innermost region that surrounds the central metal, while the outer sphere is the region surrounding the inner coordination sphere.

4. Why is the inner sphere important to us?

The inner sphere is important to us because it is essential for understanding stability, reactivity, selectivity, and the function of metalloproteins.

Image Courtesy:

1. “Inner Vs Outer Sphere Mechanisms” By Alieros – Own work (CC BY-SA 4.0) via Commons Wikimedia

About the Author: Hasini A

Hasini is a graduate of Applied Science with a strong background in forestry, environmental science, chemistry, and management science. She is an amateur photographer with a keen interest in exploring the wonders of nature and science.

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