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

Smruti B. Amin, Tobin J. Marks

Research output: Contribution to journalReview article

146 Citations (Scopus)


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. Avariety 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.

Original languageEnglish
Pages (from-to)2006-2025
Number of pages20
JournalAngewandte Chemie - International Edition
Issue number11
Publication statusPublished - Feb 28 2008



  • Homogeneous catalysis
  • Lanthanides
  • Polymerization
  • Synthesis design
  • Transition metals

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this