A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. Pd II -catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates a,w-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a p-h 3 interaction for the case of VF.Telechelic polymers, composed of chains with two distinctive endgroups, are of broad relevance. They are used, for example, as cross-linkers, chain extenders, and to form block copolymers and defined networks.[1] Syntheses of telechelic polymers with well-defined structures from simple feedstocks such as ethylene are, however, rare. At the same time, telechelic polyethylenes (PEs) are finding increasing attention. They combine attractive properties such as crystallizability, chemical stability, a hydrophobic nature and compatibility with polyolefin materials. [2] Existing approaches to produce telechelic PE comprise: 1) partial hydrogenation of polybutadiene followed by ethenolysis (metathesis degradation with ethylene); [3] 2) ring-opening metathesis polymerization (ROMP) of cyclic olefins in the presence of a key chain transfer agent (CTA) containing reactive groups followed by functionalization and hydrogenation; [4] 3) living coordinative polymerization of ethylene using functionalized initiators followed by chainend-capping agent in the absence of ethylene; [5] 4) catalyzed chain growth (CCG) polymerization [6] of ethylene using the combination of a neodymium catalyst [7] and a well-designed di(10-undecenyl)magnesium as a CTA followed by treatment with iodine and then t

A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. Pd II -catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates a,w-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a p-h 3 interaction for the case of VF.Telechelic polymers, composed of chains with two distinctive endgroups, are of broad relevance. They are used, for example, as cross-linkers, chain extenders, and to form block copolymers and defined networks.[1] Syntheses of telechelic polymers with well-defined structures from simple feedstocks such as ethylene are, however, rare. At the same time, telechelic polyethylenes (PEs) are finding increasing attention. They combine attractive properties such as crystallizability, chemical stability, a hydrophobic nature and compatibility with polyolefin materials. [2] Existing approaches to produce telechelic PE comprise: 1) partial hydrogenation of polybutadiene followed by ethenolysis (metathesis degradation with ethylene); [3] 2) ring-opening metathesis polymerization (ROMP) of cyclic olefins in the presence of a key chain transfer agent (CTA) containing reactive groups followed by functionalization and hydrogenation; [4] 3) living coordinative polymerization of ethylene using functionalized initiators followed by chainend-capping agent in the absence of ethylene; [5] 4) catalyzed chain growth (CCG) polymerization [6] of ethylene using the combination of a neodymium catalyst [7] and a well-designed di(10-undecenyl)magnesium as a CTA followed by treatment with iodine and then t