β-Diketiminate complexes of Group 4: Active complexes for the isomerization of α-olefins and the polymerization of propylene towards elastomeric polypropylene

Ella Shaviv, Mark Botoshansky, Moris S. Eisen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

42 Scopus citations

Abstract

The β-diketiminate lithium ligand [{N(SiMe3)C(Ph)} 2CH][Li] reacted with Group 4 metal salts (Ti and Zr) to yield the complexes [{N(SiMe3)C(Ph)}2CH] 2TiCl2 (5) and [{N(SiMe3)C(Ph)} 2CH][N(SiMe3)C(Ph)NC(Ph)CH(SiMe3)] ZrCl2 (6). The crystal structure of 6 shows that one of the two ketamidinate ligands undergoes an isomerization to the corresponding substituted benzamidinate. A mechanism for the catalyzed isomerization of the β-diketiminate ligand is presented. Complex 5 was found to be active in the polymerization of propylene, producing remarkably high-molecular weight (>100,000 g mol-1) elastomeric polymer, whereas the zirconium complex was found inactive. Complex 5, and surprisingly complex 6, were found to be active catalysts, in the presence of MAO (methylalumoxane), for the isomerization of aliphatic olefins (1-octene, allylbenzene). Each complex catalyzed the olefins by different mechanisms. Kinetic studies for the isomerization of allylbenzene by complex 5 show that the reaction rate follows a first order in both catalyst and olefin concentrations with Δ H =14.7(4) kcal mol-1 and Δ S =-33(1) e.u. These findings support the epimerization mechanism of the last inserted monomer that is proposed for as the primary cause for the elastomeric properties of polypropylene produced by this complex. In addition, we show how complementary isomerization studies of α-olefins shed light on the polymerization mechanism.

Original languageEnglish
Pages (from-to)165-180
Number of pages16
JournalJournal of Organometallic Chemistry
Volume683
Issue number1
DOIs
StatePublished - 7 Oct 2003
Externally publishedYes

Keywords

  • Diketiminates
  • Elastomeric polypropylene
  • Isomerization
  • Polymerization
  • Titanium
  • X-ray structure
  • Zirconium

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