C-H Activation by Isolable Cationic Bis(phosphine) Cobalt(III) Metallacycles

J Am Chem Soc. 2022 Oct 19;144(41):19186-19195. doi: 10.1021/jacs.2c08865. Epub 2022 Oct 4.

Abstract

Five- and six-coordinate cationic bis(phosphine) cobalt(III) metallacycle complexes were synthesized with the general structures, [(depe)Co(cycloneophyl)(L)(L')][BArF4] (depe = 1,2-bis(diethylphosphino)ethane; cycloneophyl = [κ-C:C-(CH2C(Me)2)C6H4]; L/L' = pyridine, pivalonitrile, or the vacant site, BAr4F = B[(3,5-(CF3)2)C6H3]4). Each of these compounds promoted facile directed C(sp2)-H activation with exclusive selectivity for ortho-alkylated products, consistent with the selectivity of reported cobalt-catalyzed arene-alkene-alkyne coupling reactions. The direct observation of C-H activation by cobalt(III) metallacycles provided experimental support for the intermediacy of these compounds in this class of catalytic C-H functionalization reaction. Deuterium labeling and kinetic studies provided insight into the nature of C-H bond cleavage and C-C bond reductive elimination from isolable cobalt(III) precursors.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes
  • Alkynes / chemistry
  • Cobalt* / chemistry
  • Deuterium
  • Ethane
  • Kinetics
  • Pyridines* / chemistry

Substances

  • Cobalt
  • phosphine
  • Deuterium
  • Pyridines
  • Alkynes
  • Alkenes
  • Ethane