Isolation of a Square Pyramidal Bis(amidophenolate)-Supported As(III)-Cation: Coordination-Induced Electromerism at...

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Materials Science

Background:

• Arsenic chemistry offers unique electronic properties.
• Redox-active ligands can modulate metal center reactivity.
• Electromerism in main group element complexes is an emerging area.

Purpose of the Study:

• To synthesize and characterize a novel arsenium cation.
• To investigate the reactivity of the arsenium cation with Lewis bases.
• To explore the potential of this system in catalysis.

Main Methods:

• Synthesis of the arsenium cation.
• Spectroscopic analysis (e.g., NMR, UV-Vis).
• X-ray crystallography for structural determination.
• Computational modeling (e.g., DFT).
• Electron Paramagnetic Resonance (EPR) spectroscopy.
• Catalytic transfer hydrogenation experiments.

Main Results:

• A distorted square pyramidal arsenium cation was successfully synthesized and characterized.
• Coordination of Lewis bases to the As(III) center induced reversible oxidation to As(V) and ligand reduction.
• This behavior represents a clear instance of base-induced electromerism.
• Single electron reduction generated a persistent ligand-centered radical, observable by EPR.
• The arsenium cation demonstrated utility as an initiator for transfer hydrogenation.

Conclusions:

• The study reports a novel arsenium cation with unique redox and structural properties.
• Base-induced electromerism in arsenic complexes is demonstrated and characterized.
• The system shows promise for applications in catalysis, specifically transfer hydrogenation.