C-C Bonding in Molecular Systems via Cross-Coupling-like Reactions Involving Noncovalently Bound Constituent Ions

Area of Science:

• Organic Chemistry
• Computational Chemistry
• Physical Chemistry

Background:

• Carbon-based molecules are fundamental to chemical and biological processes.
• Molecular complexity increases through carbon-carbon bond formation.
• Cross-coupling reactions involving ion pairs are key mechanisms.

Purpose of the Study:

• Investigate an uncommon cross-coupling mechanism involving noncovalent ion interactions.
• Analyze the effect of alkali-halide ion pairs on C-C bond formation in halocarbons.
• Explore how ion proximity and bonding modes influence reaction pathways.

Main Methods:

• Utilized ab initio computational studies to model reaction energy barriers.
• Examined various reaction channels, including carbon-halogen bond cleavage relative to C-C bond formation.
• Assessed the impact of ion pair proximity on reaction dynamics.

Main Results:

• Observed significant alterations in energy barriers due to the presence of ion pairs.
• Demonstrated that ion pairs can switch the relative heights of energy barriers.
• Identified distinct reaction pathways influenced by ion pair interactions.

Conclusions:

• Ion pairs can significantly modify energy barriers in C-C bond formation reactions.
• The proximity and bonding of ion pairs play a critical role in determining reaction outcomes.
• These findings suggest potential for catalyst-free facilitation of halocarbon cross-coupling reactions.