Functionalization of β-Alkylcorrole Using Ag(I) Salts

Area of Science:

• Coordination Chemistry
• Organometallic Chemistry
• Porphyrinoid Synthesis

Background:

• The coordination chemistry of β-alkylcorroles is underdeveloped compared to triarylcorroles.
• Existing synthetic routes for silver insertion into triarylcorroles were explored for β-alkylcorroles.

Purpose of the Study:

• Investigate the synthesis of silver complexes with β-alkylcorroles.
• Understand the reactivity differences between β-alkylcorroles and triarylcorroles in metalation reactions.

Main Methods:

• Reaction of β-alkylcorroles with silver acetate (AgOAc) in pyridine and acetonitrile.
• Characterization using UV-vis spectroscopy, 1H NMR, mass spectrometry, and single-crystal X-ray crystallography.
• Exploration of silver nitrate (AgNO2), silver hexafluorophosphate (AgPF6), and silver nitrate (AgNO3) as alternative silver sources.

Main Results:

• AgOAc in pyridine led to oxocorrole formation.
• Acetonitrile yielded oxocorroles and other products, including an acetate-functionalized oxocorrole and a meso-substituted silver complex.
• AgNO2 resulted in rapid meso-nitration, followed by silver insertion into the trinitrocorrole.
• Silver salts with non-nucleophilic anions did not result in metalation or meso-functionalization.

Conclusions:

• β-alkylcorroles exhibit distinct reactivity compared to triarylcorroles.
• Silver coordination into the β-alkylcorrole core is hindered and often requires prior peripheral substitution.
• The synthetic pathway for silver complexes of β-alkylcorroles is complex and prone to oxidation and functionalization.