Organoboron-mediated polymerizations

Area of Science:

• Polymer Chemistry
• Organometallic Chemistry
• Catalysis

Background:

• Organoboron compounds have emerged as versatile tools in synthesis and catalysis.
• Their application in polymer science has expanded significantly over the last two decades.
• This review focuses on organoboron-mediated polymerization strategies.

Purpose of the Study:

• To review achievements in organoboron-mediated polymerizations over several decades.
• To elucidate the underlying mechanisms based on polymerization modes.
• To highlight the synthesis of various polymer topologies using organoboron compounds.

Main Methods:

• Free radical polymerization using alkylborane/O2 systems.
• Lewis pair polymerization of polar monomers with organoboron/Lewis base combinations.
• Ring-opening (co)polymerization catalyzed by organoboron Lewis pairs and bifunctional catalysts.
• Polyhomologation of ylides initiated by organoboranes.

Main Results:

• Controlled/living radical polymerization achieved via optimized alkylborane structures.
• Lewis pair polymerization enables the synthesis of polymers from polar monomers.
• Organoboron catalysts facilitate efficient ring-opening polymerization of cyclic monomers.
• Polyhomologation yields functional polyethylene with diverse topologies.
• Various polymer architectures, including linear, block, cyclic, and graft polymers, are produced.

Conclusions:

• Organoboron compounds offer powerful, metal-free routes for diverse polymerizations.
• Understanding these mechanisms inspires the design of advanced organoboron catalysts.
• This work benefits the polymer chemistry and organometallic/organocatalysis communities.