Polymerization of Alkyl Diazoacetates Initiated with Pd Complexes

Abstract

SummaryPd‐initiated polymerization of alkyl diazoacetates as an effective methodology to prepare carbon‐carbon (CC) main chain polymers bearing a substituent on every main chain carbon is described. (NHC)Pd/borate (NHC = N‐heterocyclic carbene) systems are efficient at affording high Mn polymers. π‐AllylPdCl‐based systems can initiate the polymerization with the number of polymer chain per Pd ratios over 1.0 because of occurrence of chain transfer, capable of affording relatively low Mn polymers in high yield. Initiation and termination mechanisms have been proposed for the latter initiating systems, based on the detailed MALDI‐TOF‐MS analyses of the low Mn products.