A computational study on the identity of the active catalyst structure for Ru(II) carboxylate assisted C–H activation in acetonitrile

Claire McMullin, Nasir Rajabi, James Hammerton

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Density Functional Theory (DFT) calculations using a consistent methodology accounting for solvation, dispersion and thermal effects have been used to study C–H activation of the simple directing group substrate 2-phenylpyridine (a-H). The computational model uses acetate (OAc) and benzene to represent the carboxylate and arene co-ligands coordinated at a Ru organometallic complex. A variety of different mechanisms ranging from cationic to neutral, ion-paired, arene free, two substrates bound, and solvent (MeCN) coordinated have been explored. Computed results indicate that the cationic pathways from “B+”, [(C6H6)Ru(OAc)(a-H)]+, and “D+6)”, [(η6-a-H)Ru(OAc)(a-H)]+, involve the lowest overall barriers to C–H activation. Consideration of solvent coordination leads to a complex variety of isomers and conformers. Here a neutral pathway with either one or two acetonitriles coordinated to the Ru centre give very low barriers to C–H activation.
Original languageEnglish
Pages (from-to)6678-6686
Number of pages9
JournalOrganic & Biomolecular Chemistry
Issue number27
Publication statusPublished - 25 Jun 2019

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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