Solvation of dichlorocarbene: complexation with aryl ethers

Area of Science:

• Organic Chemistry
• Photochemistry
• Computational Chemistry

Background:

• Dichlorocarbene (CCl(2)) is a highly reactive intermediate.
• Understanding its interactions with various substrates is crucial for reaction control.

Purpose of the Study:

• To investigate the formation and characterization of dichlorocarbene complexes with aromatic ethers and esters.
• To determine the effect of these complexes on the reactivity of dichlorocarbene.

Main Methods:

• Laser flash photolysis of dichlorodiazirine to generate dichlorocarbene.
• UV-vis spectroscopy for complex visualization.
• Density functional theory (DFT) calculations for structural and energetic analysis.

Main Results:

• Formation of pi- and O-ylidic complexes between dichlorocarbene and aromatic ethers/esters was observed.
• These complexes significantly retarded the addition of dichlorocarbene to tetramethylethylene (factors of 18-152).
• Non-aromatic ethers did not form observable complexes and had minimal effect on reactivity.

Conclusions:

• Aromaticity plays a key role in the stabilization of dichlorocarbene complexes.
• Transient complex formation can effectively modulate the reactivity of dichlorocarbene.
• DFT calculations support the experimental findings and provide insights into complex structures.