Electron transfer and catalysis with high-valent metal-oxo complexes

Area of Science:

• Inorganic Chemistry
• Photochemistry
• Catalysis

Background:

• High-valent metal-oxo complexes are key intermediates in oxidation reactions.
• Their generation and reactivity are crucial for catalytic oxygenation processes.

Purpose of the Study:

• To summarize catalytic and photocatalytic reactions involving high-valent metal-oxo complexes.
• To highlight the use of water or dioxygen as oxygen sources for substrate oxygenation.

Main Methods:

• Reductive activation of dioxygen with metal complexes and reductants.
• Photoinduced electron transfer from substrates to metal complexes.
• Proton-coupled electron-transfer oxidation of metal complexes with oxidants and water.

Main Results:

• High-valent metal-oxo complexes can be generated through diverse electron-transfer pathways.
• Metal complexes can act as photocatalysts or catalysts for oxygenation.
• Weaker oxidants can be employed in photocatalytic systems.

Conclusions:

• Catalytic and photocatalytic oxygenation using high-valent metal-oxo complexes are versatile.
• Water and dioxygen serve as effective oxygen sources.
• This perspective provides a summary of these important reactions.