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New non-cyclopentadienyl organolanthanide catalysts

New non-cyclopentadienyl organolanthanide catalysts

Heimo Wölfle (ORCID: )
  • Grant DOI 10.55776/J2597
  • Funding program Erwin Schrödinger
  • Status ended
  • Start September 1, 2006
  • End November 30, 2007
  • Funding amount € 62,900

Disciplines

Chemistry (100%)

Keywords

    Organometallic chemistry, Lanthanides, Ligand design, Homogenous catalysts, Polymerization

Abstract

In the proposed research of this project, two new families of homogeneous, non-cyclopentadienyl organolanthanide catalysts of the general formula L-LnX 2 will be synthesized and evaluated with regard to their performance as polymerization catalysts of olefins, acrylates, and lactones. In organolanthanide chemistry, very large multidentate ligands are in general necessary to stabilize these highly Lewis acidic, chalco- and pnictophilic lanthanide metals Ln = Y, La, Nd, Sm, Yb, Lu as monomeric chelate complexes, and to ensure an optimized ligand sphere for the envisioned catalytic applications. The first family of new organolanthanide catalysts will comprise L-LnX 2 metal complexes with monoanionic, atrane-like, constrained geometry-type, tri- and tetradentate triptyceneimine ligands of tunable steric shielding due to the number and steric bulk of the imino substituents. The second family will comprise L-LnX 2 metal complexes with mono- or dianionic, chiral, pincer-type, tridentate bissulfoximine ligands of tunable steric shielding due to their variable imino substituents. In both families of catalysts, the coligand X-which is directly involved in the electrophilic activation step in the catalytic cycle-will be varied and optimized according to established methods in coordination chemistry and according to the polymerization reaction under study. Both apolar (olefins) and polar (metacrylates, lactones) monomers will be polymerized with these new organolanthanide catalysts. Due to the novel intrinsic shape, size, and donor-site geometry of the triptycene and bissulfoximine ligand architectures two new families of monomeric organolanthanide polymerization catalysts of high activity and improved chemo- and stereoselectivity will be obtained.

Research institution(s)
  • University of California Berkeley - 100%
  • Universität Innsbruck - 10%

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