d0/fn-mediated ring-opening Ziegler polymerization (ROZP) and copolymerization with mono- and disubstituted methylenecyclopropanes. Diverse mechanisms and a new chain-capping termination process

Tryg R. Jensen, James J. O'Donnell, Tobin J. Marks

Research output: Contribution to journalArticle

23 Citations (Scopus)


The mono- and disubstituted methylenecyclopropane derivatives 2-phenyl-1-methylene-cyclopropane (A) and 7-methylenebicyclo[4.1.0]heptane (B) have been successfully implemented in ring-opening Ziegler polymerization. Homogeneous ethylene + 2-phenyl-1-methylenecyclopropane (A) random copolymerizations are mediated efficiently by the single-site catalysts Cp*2ZrMe+B(C6F5) 4-, [Cp*2LuH]2, [Cp*2SmH]2, and [Cp*2 YH]2 (Cp* = C5Me5) to produce a copolymer (C) with A enchained in a ring-opened fashion. Single-site coordinative polymerization of 7-methylenebicyclo[4.1.0]heptane (B) proceeds via either ring-opened or ring-unopened pathways. In the presence of Cp*2ZrMe+ MeB(C6F5) 3- at 0°C, B undergoes polymerization to afford the insoluble, ring-unopened homopolymer D, which was characterized by CPMAS NMR, DSC, elemental analysis, FTIR, TGA, and XRD. The melting point of polymer D lies above its decomposition temperature (> 300°C). Random copolymerizations of B and ethylene mediated by Cp*2 ZrMe+MeB(C6F5)3- at room temperature result in polymer E, a polyethylene capped by a ring-opened B fragment. The formation of B-capped polymer E is a consequence of a new chain transfer mechanism, as evidenced by a linear relationship between Mn and [B]-1. The rate constant for insertion of ethylene is ∼25× greater than the rate constant for insertion of monomer B into the metal-alkyl bond. Random copolymers (F) of ring-opened B and ethylene are produced when the catalysts Me2Si(Me4C5)(tBuN)ZrMe2, Me2Si(Me4C5)(tBuN)TiMe2 (activated by either (C6H5)3C+ B(C6F5)4- or B(C6F5)3), and [Cp*2LuH]2 are employed.

Original languageEnglish
Pages (from-to)740-754
Number of pages15
Issue number4
Publication statusPublished - Feb 16 2004


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this