A reusable unsupported rhenium nanocrystalline catalyst for acceptorless dehydrogenation of alcohols through γ-C-H activation

Jing Yi, Jeffrey T. Miller, Dmitry Y. Zemlyanov, Ruihong Zhang, Paul J. Dietrich, Fabio H. Ribeiro, Sergey Suslov, Mahdi M. Abu-Omar

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH4ReO4 under mild conditions in neat alcohol. The unsupported Re NPs convert secondary and benzylic alcohols to ketones and aldehydes, respectively, through catalytic acceptorless dehydrogenation (AD). The oxidant- and acceptor-free neat dehydrogenation of alcohols to obtain dihydrogen gas is a green and atom-economical process for making carbonyl compounds. Secondary aliphatic alcohols give quantitative conversion and yield. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Re K-edge X-ray absorption near-edge structure (XANES), and X-ray absorption fine structure (EXAFS) data confirmed the characterization of the Re NPs as metallic rhenium with surface oxidation to rhenium(IV) oxide (ReO2). Isotope labeling experiments revealed a novel γ-CH activation mechanism for AD of alcohols. Active particles: A rhenium nanoparticle (Re NP) catalyst is generated from NH4ReO4 under mild solution conditions in neat 3-octanol at 180°C. The resulting Re NPs catalyze acceptorless dehydrogenation of alcohols through a novel C-H activation pathway, and are fully recyclable.

Original languageEnglish
Pages (from-to)833-836
Number of pages4
JournalAngewandte Chemie - International Edition
Volume53
Issue number3
DOIs
Publication statusPublished - 2014
Externally publishedYes

Fingerprint

Rhenium
Dehydrogenation
Alcohols
Chemical activation
Catalysts
X ray absorption
X-Rays
Isotope Labeling
Octanols
Photoelectron Spectroscopy
Carbonyl compounds
Ketones
Transmission Electron Microscopy
Oxidants
Aldehydes
Nanoparticles
Isotopes
Oxides
Labeling
Gases

Keywords

  • alcohols
  • dehydrogenation
  • heterogeneous catalysis
  • nanoparticles
  • rhenium

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

A reusable unsupported rhenium nanocrystalline catalyst for acceptorless dehydrogenation of alcohols through γ-C-H activation. / Yi, Jing; Miller, Jeffrey T.; Zemlyanov, Dmitry Y.; Zhang, Ruihong; Dietrich, Paul J.; Ribeiro, Fabio H.; Suslov, Sergey; Abu-Omar, Mahdi M.

In: Angewandte Chemie - International Edition, Vol. 53, No. 3, 2014, p. 833-836.

Research output: Contribution to journalArticle

Yi, Jing ; Miller, Jeffrey T. ; Zemlyanov, Dmitry Y. ; Zhang, Ruihong ; Dietrich, Paul J. ; Ribeiro, Fabio H. ; Suslov, Sergey ; Abu-Omar, Mahdi M. / A reusable unsupported rhenium nanocrystalline catalyst for acceptorless dehydrogenation of alcohols through γ-C-H activation. In: Angewandte Chemie - International Edition. 2014 ; Vol. 53, No. 3. pp. 833-836.
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