Dinitrogen photoactivation: status quo and future perspectives

Area of Science:

• Inorganic Chemistry
• Photochemistry
• Materials Science

Background:

• Thermal activation of dinitrogen (N₂) is well-established with various transition metals.
• Photocleavage of the N-N bond using light is significantly less explored.
• Six known transition metal complexes cleave N₂ via photoactivation.

Purpose of the Study:

• To review molecular complexes capable of dinitrogen photocleavage.
• To discuss mechanistic insights into the photoactivation process.
• To propose a scheme for identifying new dinitrogen photoactivatable complexes.

Main Methods:

• Literature review of existing molecular complexes.
• Analysis of experimental studies on dinitrogen photocleavage.
• Examination of computational studies on photoactivation mechanisms.

Main Results:

• Six complexes binding N₂ in a linear μ-η¹:η¹-end-on fashion are known to photocleave dinitrogen.
• Photoactivation involves absorption of a photon and relaxation from an excited state.
• Mechanistic insights suggest pathways facilitating protonation of bridging nitrogen atoms.

Conclusions:

• Dinitrogen photocleavage is a viable, albeit less explored, activation strategy.
• Understanding photoactivation mechanisms is key to designing new catalysts.
• The proposed scheme aids in identifying novel complexes for dinitrogen photoactivation.