title: Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization.
abstract: A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII-catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-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 π-η3interaction for the case of VF.
authors.affiliation: Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Universitätsstrasse 10, 78457, Konstanz, Germany.
authors.forename: Zhongbao
authors.identifier: 0000-0003-3052-4596
authors.initials: Z
authors.lastname: Jian
authors.affiliation: Physical Sciences and Engineering, Kaust Catalysis Center, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Laura
authors.initials: L
authors.lastname: Falivene
authors.affiliation: Department of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano, SA, Italy.
authors.forename: Giusi
authors.initials: G
authors.lastname: Boffa
authors.affiliation: Department of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano, SA, Italy.
authors.forename: Sheila Ortega
authors.initials: SO
authors.lastname: Sánchez
authors.affiliation: Department of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano, SA, Italy. lcaporaso@unisa.it.
authors.forename: Lucia
authors.initials: L
authors.lastname: Caporaso
authors.affiliation: Department of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084, Fisciano, SA, Italy.
authors.forename: Alfonso
authors.initials: A
authors.lastname: Grassi
authors.affiliation: Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Universitätsstrasse 10, 78457, Konstanz, Germany. stefan.mecking@uni-konstanz.de.
authors.forename: Stefan
authors.identifier: 0000-0002-6618-6659
authors.initials: S
authors.lastname: Mecking
keywords: DFT calculations; insertion; palladium; polyethylene; telechelic polymers