Mild sp2Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory

Samantha Lau, Bryan Ward, Xueer Zhou, Andrew J. P. White, Ian J. Casely, Stuart Alan Macgregor, Mark R. Crimmin

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)
27 Downloads (Pure)

Abstract

The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)2(N2)2(PCy3)2] (1) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp2C-O bond activation at temperatures below 40 °C. DFT studies support a low-energy Ru(II)/Ru(IV) pathway for C-O bond activation: oxidative addition of the C-O bond to Ru(II) occurs in an asynchronous manner with Ru-C bond formation preceding C-O bond breaking. Alternative pathways based on a Ru(0)/Ru(II) couple are competitive but less accessible due to the high energy of the Ru(0) precursors. Both experimentally and by DFT calculations, sp2C-H bond activation is shown to be more facile than sp2C-O bond activation. The kinetic preference for C-H bond activation over C-O activation is attributed to unfavorable approach of the C-O bond toward the metal in the selectivity determining step of the reaction pathway.

Original languageEnglish
Pages (from-to)3654-3663
Number of pages10
JournalOrganometallics
Volume36
Issue number18
Early online date14 Sep 2017
DOIs
Publication statusPublished - 25 Sep 2017

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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