Versatile pathways for in situ polyolefin functionalization with heteroatoms: catalytic chain transfer

Angewandte Chemie
Smruti B Amin, Tobin J Marks

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.

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Citations

Oct 19, 2011·Accounts of Chemical Research·Staci L WegenerPeter C Stair
Feb 9, 2013·Chemical Reviews·Andreia ValentePhilippe Zinck
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