Abstract
We describe the polymerization of a variety of diazocarbonyl compounds initiated with Pd complexes. Relatively low molecular weight polymers (Mn = ca. 2000) were obtained by the polymerization of diazoacetates, diazoketones, and diazoacetamides initiated with PdCl2. On the other hand, the polymerization of diazoacetates by (NHC)Pd/borate and π-allyl-PdCl-based systems can afford high molecular weight polymers (Mn > 10000). Chain-end structure analyses by using MALDI-TOF-MS was used to elucidate initiation and termination mechanisms for the π-allyl-PdCl-based systems. Polymerization of hydroxy-containing diazoacetates resulted in the formation of unique polymers with densely accumulated hydroxy groups around their C-C main chains.
