Where and How Does an Organic Molecule Having a C-X Bond Release X

Area of Science:

• Computational Chemistry
• Organic Chemistry
• Materials Science

Background:

• Orthoamides are a class of organic compounds with potential applications as anion-releasing agents.
• Understanding the mechanisms of anion release is crucial for designing novel functional materials.

Purpose of the Study:

• To conduct a comparative DFT study on hydride or fluoride release from orthoamides and related organic compounds.
• To investigate the factors influencing anion release, particularly the role of electronic interactions.
• To elucidate the mechanisms of anion removal from orthoamides.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to study anion release.
• Comparative analysis of hydride/fluoride release from orthoamides, fluorine derivatives, and simple organic compounds.
• Investigation of reaction mechanisms with Lewis acids (e.g., BH3, BF3) and protonation.

Main Results:

• Orthoamides demonstrate significantly easier hydride or fluoride anion release compared to other studied organic compounds.
• Three simulated orthoamides with a C-F bond spontaneously released fluoride anions in polar solvents.
• pπ-pπ interactions in carbocations were identified as a critical factor for efficient anion release.
• Mechanisms for hydride and fluoride removal via reaction with BH3/BF3 and protonation were established.
• Various substituents on orthoamides were shown to readily leave as anions upon reaction with Lewis acids.

Conclusions:

• Orthoamides are superior hydride/fluoride anion releasing agents compared to other organic compounds.
• pπ-pπ interactions in carbocations are paramount for designing effective anion-releasing agents.
• Orthoamides offer a versatile platform for generating various anions upon reaction with Lewis acids.