Catalytic Dehydrogenation of Alkanes by PCP-Pincer Iridium Complexes Using Proton and Electron Acceptors

Arun Dixith Reddy Shada, Alexander J.M. Miller, Thomas J. Emge, Alan S. Goldman

Research output: Contribution to journalArticlepeer-review

Abstract

Dehydrogenation to give olefins offers the most broadly applicable route to the chemical transformation of alkanes. Transition-metal-based catalysts can selectively dehydrogenate alkanes using either olefinic sacrificial acceptors or a purge mechanism to remove H2; both of these approaches have significant practical limitations. Here, we report the use of pincer-ligated iridium complexes to achieve alkane dehydrogenation by proton-coupled electron transfer, using pairs of oxidants and bases as proton and electron acceptors. Up to 97% yield was achieved with respect to oxidant and base, and up to 15 catalytic turnovers with respect to iridium, using t-butoxide as base coupled with various oxidants, including oxidants with very low reduction potentials. Mechanistic studies indicate that (pincer)IrH2 complexes react with oxidants and base to give the corresponding cationic (pincer)IrH+ complex, which is subsequently deprotonated by a second equivalent of base; this affords (pincer)Ir which is known to dehydrogenate alkanes and thereby regenerates (pincer)IrH2.

Original languageEnglish
Pages (from-to)3009-3016
Number of pages8
JournalACS Catalysis
DOIs
Publication statusAccepted/In press - 2021

Keywords

  • alkane dehydrogenation
  • C-H activation
  • iridium catalysis
  • pincer complexes
  • proton-coupled electron transfer

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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