Threefold reactivity of a COF-embedded rhenium catalyst: reductive etherification, oxidative esterification or...

Area of Science:

• Organometallic Chemistry
• Materials Science
• Catalysis

Background:

• Rhenium(I) complexes are versatile homogeneous catalysts.
• Covalent organic frameworks (COFs) offer tunable porous structures for catalyst immobilization.
• Controlling catalyst reactivity within confined environments is crucial for selective synthesis.

Purpose of the Study:

• To investigate the impact of a covalent organic framework (COF) on the reactivity of a novel Re(I) catalyst.
• To explore the modulation of catalytic activity and selectivity by the COF's local environment.
• To demonstrate the potential of COFs in tailoring homogeneous catalyst performance.

Main Methods:

• Synthesis and characterization of the Re(I) catalyst [Re(^C12Anth-py₂)(CO)₃Br].
• Integration of the Re(I) catalyst within the TFB-BD covalent organic framework (COF).
• Evaluation of catalytic activity in reductive etherification, oxidative esterification, and transfer hydrogenation under different conditions (embedded, homogeneous, co-incubated).

Main Results:

• The Re(I) catalyst exhibited distinct reactivity depending on its environment.
• Catalyst embedded in TFB-BD showed specific activity, differing from homogeneous or co-incubated states.
• The COF TFB-BD significantly modulated the catalytic pathways of the Re(I) complex.

Conclusions:

• Covalent organic frameworks (COFs) can drastically alter the reactivity of homogeneous catalysts.
• The local environment provided by COFs offers a powerful strategy for tuning catalyst performance.
• This work opens new avenues for designing advanced catalytic systems using COF-supported catalysts.