Reduction Polymerization of CO₂ with Phenylene Silanes Catalyzed by Single Component B(C₆F₅)₃

Area of Science:

• Polymer Chemistry
• Organometallic Chemistry
• Green Chemistry

Background:

• Carbon dioxide (CO2) is an abundant yet inert C1 resource, posing challenges for its utilization.
• Developing efficient methods for CO2 conversion into valuable materials is a key goal in sustainable chemistry.

Purpose of the Study:

• To report the unprecedented polymerization of CO2 with silanes.
• To develop a tandem polymerization system for advanced polysiloxane synthesis.
• To elucidate the catalytic mechanism using density functional theory.

Main Methods:

• Catalytic polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3.
• Copolymerization with functionalized phenylene silanes.
• Tandem polymerization integrating Piers-Rubinsztajn reaction.
• Density functional theory (DFT) calculations for mechanistic insights.

Main Results:

• Successful synthesis of poly(silphenylene siloxane) from CO2 and silanes with methane release.
• Extension of copolymerization to functionalized monomers.
• Creation of a tandem system for super thermal resistant poly(siloxane-co-silphenylene siloxane)s.
• DFT revealed HB(C6F5)2 as the active species in CO2 reduction.

Conclusions:

• A novel catalytic system for CO2 polymerization into polysiloxanes has been established.
• The findings open new avenues for CO2 utilization in advanced polymer synthesis.
• The developed tandem system enables the production of high-performance, thermally stable polysiloxanes.