Catalysts for the Living Insertion Polymerization of Alkenes: Access to New Polyolefin Architectures Using Ziegler-Natta Chemistry

Coordination–insertion polymerization systems have long been superior to their anionic, cationic, and radical polymerization counterparts with regard to stereochemical control. However, until five years ago, these metal‐based insertion methods were inferior to ionic and radical mechanisms in the category of living polymerization, which is simply a polymerization that occurs with rapid initiation and negligible chain termination or transfer. In the last half decade, the living insertion polymerization of unactivated olefins has emerged as a powerful tool for the synthesis of new polymer architectures. Materials available today by this route range from simple homopolymers such as linear and branched polyethylene, to atactic or tactic poly(α‐olefins), to end‐functionalized polymers and block copolymers. This review article summarizes recent developments in this rapidly growing research area at the interface of synthetic and mechanistic organometallic chemistry, polymer chemistry, and materials science. While special emphasis is placed on polymer properties and novel polymeric architectures, most of which were inaccessible just a decade ago, important achievements with respect to ligand and catalyst design are also highlighted. Polyolefins are ubiquitous materials in everyday life: Although these polymers are traditionally synthesized by heterogeneous transition‐metal catalysts, recent advances in single‐site catalysts have given birth to a wide array of new materials of precise stereochemistry (see picture). Although olefin‐polymerization techniques are superior to their ionic and radical counterparts regarding stereochemical control, they have been inferior in the category of living polymerization. Recent advances in alkene‐polymerization catalysts are rapidly eliminating this deficit.