Abstract
The recent developments in organoborane initiated C1 polymerization (chain grows by one atom at a time) of ylides opens unique horizons towards well-defined/perfectly linear polymethylenes (equivalent to polyethylenes, PE) and PE-based complex macromolecular architectures. The general mechanism of C1 polymerization (polyhomologation) involves the formation of a Lewis complex between a methylide (monomer) and a borane (initiator), followed by migration/insertion of a methylene into the initiator to afford, after oxidation/hydrolysis, OH-terminated polyethylenes (PE-OH). Post-functionalization/modification of PE-OH in combination with controlled/living radical polymerization techniques provides unique well-defined PE-based polymer architectures. A few examples will be given to show the importance of this partnership.