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Published online 7 November 2013;
10.1126/science.1242642
REPORTS
The durability and copious supply of iron salts
coupled with their environmentally benign nature
and low toxicity make them ideal catalysts. Re-
cently, structurally well-defined molecular iron
complexes have been applied successfully in con-
texts where previously noble metals were required
(9–19). However, most of these homogeneous
complexes are rather sensitive and/or incorporate
sophisticated (and thus synthetically demanding)
ligand systems. In contrast, heterogeneous iron
oxides are extremely stable and can be easily re-
cycled. Important applications of heterogeneous
Nanoscale Fe2O3-Based Catalysts
for Selective Hydrogenation of
Nitroarenes to Anilines
Rajenahally V. Jagadeesh,1 Annette-Enrica Surkus,1 Henrik Junge,1
Marga-Martina Pohl,1 Jörg Radnik,1 Jabor Rabeah,1 Heming Huan,2
Volker Schünemann,2 Angelika Brückner,1 Matthias Beller1*
Production of anilines—key intermediates for the fine chemical, agrochemical, and pharmaceutical iron catalysts include the production of olefins
industries—relies on precious metal catalysts that selectively hydrogenate aryl nitro groups in through the Fischer-Tropsch process (20, 21) and
the presence of other easily reducible functionalities. Herein, we report convenient and stable iron the hydrogenation of CO (22). Unfortunately, these
oxide (Fe2O3)–based catalysts as a more earth-abundant alternative for this transformation.
Pyrolysis of iron-phenanthroline complexes on carbon furnishes a unique structure in which
the active Fe2O3 particles are surrounded by a nitrogen-doped carbon layer. Highly selective
known catalysts work under drastic conditions
(>275°C) and are therefore of limited use for the
refinement of more complex substrates. In this
hydrogenation of numerous structurally diverse nitroarenes (more than 80 examples) proceeded in context, we report special iron oxide–based cat-
good to excellent yield under industrially viable conditions.
alysts that allow for a general and highly selective
hydrogenation of nitroarenes under comparably
eginning in the 1950s, the development ranging from the laboratory bench to the indus- mild conditions. The resulting anilines consti-
of organometallic catalysts proceeded to trial manufacture of fine and bulk chemicals. This tute key building blocks for the synthesis of fine
revolutionize organic synthesis at scales success was mainly due to the use of noble metal (agrochemicals, dyes, pigments, and pharmaceut-
complexes—for example, palladium, rhodium, ru- icals) as well as bulk chemicals (polymers) (23, 24).
B
1Leibniz-Institut für Katalyse e.V. an der Universität Rostock,
Albert-Einstein Strasse 29a, D-18059 Rostock, Germany 2Tech-
nische Universität Kaiserslautern, Fachbereich Physik, Erwin-
Schrödinger-Strasse 46, D-67663 Kaiserslautern, Germany.
thenium, and iridium (1). However, the high price In particular, anilines used in life science applications
and limited availability of these precious metals are often structurally complex molecules decorated
(2) have spurred interest in catalysis with more with diverse functional groups. Thus, achieving
earth-abundant alternatives, especially iron (3–8). high chemoselectivity is of crucial importance for
*Corresponding author. E-mail: matthias.beller@catalysis.de
1073