title: Versatile pathways for in situ polyolefin functionalization with heteroatoms: catalytic chain transfer.
abstract: Chain-transfer processes represent highly effective chemical means to achieve selective, in situ d- and f-block-metal catalyzed functionalization of polyolefins. A diverse variety of electron-poor and electron-rich chain-transfer agents, including silanes, boranes, alanes, phosphines, and amines, effect efficient chain termination with concomitant carbon-heteroelement bond formation during single-site olefin-polymerization processes. High polymerization activities, control of polyolefin molecular weight and microstructure, and selective chain functionalization are all possible, with distinctly different mechanisms operative for the electron-poor and electron-rich reagents. A variety of metal centers (early transition metals, lanthanides, late transition metals) and single-site ancillary ligand arrays (metallocene, half-metallocene, non-metallocene) are able to mediate these selective chain-termination/functionalization processes.
authors.affiliation: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
authors.forename: Smruti B
authors.initials: SB
authors.lastname: Amin
authors.forename: Tobin J
authors.initials: TJ
authors.lastname: Marks