The Corrole Radical.

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Materials Science

Background:

• Corroles are macrocyclic ligands structurally related to porphyrins.
• Tungsten complexes with corrole ligands are less explored.
• Steric and electronic properties of corrole ligands influence complex stability and reactivity.

Purpose of the Study:

• To investigate the reaction of 5,10,15-trimesitylcorrole with tungsten precursors.
• To characterize the resulting tungsten-corrole species.
• To explore the coordination chemistry of novel corrole derivatives.

Main Methods:

• Synthesis of 5,10,15-trimesitylcorrole.
• Reaction with tungsten hexachloride and tungsten hexacarbonyl.
• X-ray crystallography for structural determination.
• Density Functional Theory (DFT) calculations.

Main Results:

• Unexpected formation of air-stable 3,17-dichloro-5,10,15-trimesitylcorrole radical (H2 cor*).
• X-ray crystallography confirmed a planarized corrole radical structure due to reduced N4 cavity steric hindrance.
• DFT calculations supported the regioselectivity of chlorination via nucleophilic attack on an oxidized macrocycle.
• The dianionic corrole radical ligand facilitated the insertion of divalent zinc(II).

Conclusions:

• The study reports a novel, stable dichloro-corrole radical.
• Planarization of the corrole radical enhances its ligand properties.
• The unique reactivity allows for the formation of unusual metal-corrole complexes, expanding coordination chemistry possibilities.