Carbon–Carbon Bond Formation in a Weak Ligand Field: Leveraging Open-Shell First-Row Transition-Metal Catalysts

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Abstract

Unique features of earth-abundant transition-metal catalysts are reviewed in the context of catalytic carbon–carbon bond-forming reactions. Aryl-substituted bis(imino)pyridine iron and cobalt dihalide compounds, when activated with alkyl aluminum reagents, form highly active catalysts for the polymerization of ethylene. Open-shell iron and cobalt alkyl complexes have been synthesized that serve as single-component olefin polymerization catalysts. Reduced bis(imino)pyridine iron and cobalt dinitrogen compounds have also been discovered that promote the unique [2+2] cycloaddition of unactivated terminal alkenes. Studies of the electronic structure support open-shell intermediates, a deviation from traditional strong-field organometallic compounds that promote catalytic C−C bond formation.

Original languageEnglish (US)
Pages (from-to)5170-5181
Number of pages12
JournalAngewandte Chemie - International Edition
Volume56
Issue number19
DOIs
StatePublished - Jan 1 2017

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • cobalt
  • cycloaddition
  • homogeneous catalysis
  • iron
  • polymerization

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