Selective Nitrogen-Atom Transfer Driven by a Highly Efficient Intersystem Crossing in the [CeON]⁺ /CH₄ System.

Area of Science:

• Inorganic Chemistry
• Physical Chemistry
• Computational Chemistry

Background:

• Understanding the reactivity of metal-containing cluster ions is crucial for catalysis and materials science.
• Gas-phase reactions provide fundamental insights into reaction pathways, uninfluenced by solvent effects.

Purpose of the Study:

• To investigate the thermal gas-phase reaction mechanism of the [CeON]+ cluster ion with methane.
• To identify the products and reaction channels involved in this transformation.
• To elucidate the electronic factors, including intersystem crossing, that govern the observed reactivity.

Main Methods:

• Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry was employed to study the gas-phase reactions.
• High-level quantum-chemical calculations were performed to explore reaction pathways and energetics.
• Comparison with related cerium-containing ions and atomic nitrogen was conducted.

Main Results:

• Nitrogen atom transfer to methane was identified as the sole reaction pathway for [CeON]+.
• Computational analysis suggests the formation of CH2NH2 or CH3NH as neutral products.
• The reaction is facilitated by a weak OCe+-N bond and efficient intersystem crossing.

Conclusions:

• The [CeON]+ ion exhibits specific nitrogen-transfer reactivity towards methane.
• Intersystem crossing plays a significant role in enabling this reaction pathway.
• Comparative analysis highlights the unique reactivity of [CeON]+ relative to other cerium species and atomic nitrogen.