Frontiers of mechanistic studies of coordination polymerization and oligomerization of α-olefins

Homogeneous single-site alkene polymerization is a “mature” field. However, this does not imply that interest to this research area fades. Moreover, armed by well understood fundamentals of single-site polymerization, researchers get more and more detailed mechanistic data, important for the improvement of the existing catalyst systems, and rational design of new effective catalysts.This review aims at summarizing the new results obtained over the last few years in unraveling the mechanisms of coordination polymerization of α-olefins and selective oligomerization of ethylene. It is mainly focused on isospecific polymerization, living polymerization, polymerization by late transition metal complexes, and selective trimerization and tetramerization of ethylene.

► Recent data on the active sites of single-site polymerization catalysts are discussed. ► New insights in the origin of living polymerization on o-fluorinated catalysts are summarized. ► Isolation of Cr self-activating ethylene trimerization catalysts gives the key to the mechanism. ► Different active species conduct selective trimerization and tetramerization of ethylene.