Premium
A Reusable Unsupported Rhenium Nanocrystalline Catalyst for Acceptorless Dehydrogenation of Alcohols through γ‐C–H Activation
Author(s) -
Yi Jing,
Miller Jeffrey T.,
Zemlyanov Dmitry Y.,
Zhang Ruihong,
Dietrich Paul J.,
Ribeiro Fabio H.,
Suslov Sergey,
AbuOmar Mahdi M.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201307665
Subject(s) - dehydrogenation , rhenium , chemistry , catalysis , nanocrystalline material , x ray photoelectron spectroscopy , xanes , extended x ray absorption fine structure , photochemistry , oxide , inorganic chemistry , absorption spectroscopy , organic chemistry , spectroscopy , chemical engineering , crystallography , physics , quantum mechanics , engineering
Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH 4 ReO 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 2 ). Isotope labeling experiments revealed a novel γ‐CH activation mechanism for AD of alcohols.