Viking Helmet Corroles: Activating Inert Oxidometal Corroles

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Chemically inert oxidometal(V) corroles (molybdenum and rhenium) were previously known.
• Ligand-exchange reactions on these corroles were not fully explored.

Purpose of the Study:

• To synthesize and characterize novel dichlorido corrole complexes.
• To investigate the reactivity of these complexes with carbon nucleophiles.
• To develop new organometallic corrole compounds with potential applications.

Main Methods:

• Ligand-exchange reactions using SiCl4.
• Optical and resonance spectroscopy.
• Density Functional Theory (DFT) calculations.
• In situ reactivity studies with carbon nucleophiles.
• Treatment with sodium cyclopentadienide.
• Structural, spectroelectrochemical, and chemical investigations.

Main Results:

• Formation of trigonal prismatic dichlorido complexes with cis-configured chlorine atoms.
• High reactivity of chlorine atoms towards nucleophilic substitution.
• Synthesis of robust molybdenum corrolocene half-sandwich complexes.
• Stabilization of an air-stable, diamagnetic low spin d2-MoIV center for the first time in corrole chemistry.
• Observation of a reversible MoIV/MoV redox couple near the Fc/Fc+ potential.

Conclusions:

• Novel dichlorido corrole complexes are readily synthesized and exhibit high reactivity.
• Molybdenum corrolocene half-sandwich complexes represent a new class of stable organometallic compounds.
• These compounds demonstrate promising potential for applications in catalysis and as redox switches due to their stable redox states.