Organometallic chemistry using partially fluorinated benzenes

Area of Science:

• Organometallic Chemistry
• Catalysis
• Fluorinated Aromatics

Background:

• Fluorobenzenes (FB) and 1,2-difluorobenzene (1,2-DiFB) are emerging as key solvents in modern chemistry.
• Their fluorine substituents decrease π-electron donation, leading to weak interactions with metal centers.

Purpose of the Study:

• To explore the utility of FB and 1,2-DiFB as non-coordinating solvents and ligands.
• To review the binding strengths and reactivity of fluorobenzene complexes.
• To highlight their potential in organic synthesis.

Main Methods:

• Review of well-defined transition metal complexes featuring fluorobenzene ligands.
• Analysis of binding trends with varying fluorination and substitution patterns.
• Survey of C-H and C-F bond activation reactions involving fluorobenzenes.

Main Results:

• Fluorobenzenes exhibit weak coordination to metal centers, functioning as non-coordinating solvents or labile ligands.
• Binding strength correlates with the degree and pattern of fluorination.
• FB and 1,2-DiFB show relative inertness but undergo C-H and C-F activation with suitable catalysts.

Conclusions:

• FB and 1,2-DiFB are versatile and relatively inert solvents for organometallic chemistry and catalysis.
• Their unique electronic properties enable their use as readily displaced ligands.
• Fluorobenzenes offer opportunities for novel synthetic transformations via C-H and C-F bond activation.