Angew Chem Int Ed Engl. 2017 May 02;56(19):5170-5181. doi: 10.1002/anie.201611959. Epub 2017 Mar 30.

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

Angewandte Chemie (International ed. in English)

Paul J Chirik

PMID: 28081286 DOI: 10.1002/anie.201611959

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.

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: cobalt; cycloaddition; homogeneous catalysis; iron; polymerization

Publication Types

• Journal Article
• Review
• Research Support, U.S. Gov't, Non-P.H.S.
• Research Support, Non-U.S. Gov't