Details

Autor(en) / Beteiligte

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

Titel

A Reusable Unsupported Rhenium Nanocrystalline Catalyst for Acceptorless Dehydrogenation of Alcohols through [gamma]-C-H Activation

Ist Teil von

• Angewandte Chemie, 2014-01, Vol.126 (3), p.852-855

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2014

Link zum Volltext

Quelle

Wiley-Blackwell Full Collection

Beschreibungen/Notizen

• Rhenium nanocrystalline particles (Re NPs), of 2nm size, were prepared from NH sub(4)ReO sub(4) 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 (ReO sub(2)). Isotope labeling experiments revealed a novel [gamma]-CH activation mechanism for AD of alcohols.Original Abstract: Aktive Partikel: Ein Rheniumnanopartikel(ReNP)-Katalysator wird ausgehend von NH sub(4)ReO sub(4) unter milden Bedingungen in reinem 3-Octanol bei 180 degree C hergestellt. Die erhaltenen ReNPs katalysieren die akzeptorfreie Dehydrierung von Alkoholen ueber einen neuen C-H-Aktivierungspfad und konnen vollstaendig zurueckgewonnen werden.