2008-Angew.-Sustainable Metal Catalysis with Iron From Rust to a Rising Star.pdf

Homogeneous Catalysis DOI: 10.1002/anie.200800012 Sustainable Metal Catalysis with Iron: From Rust to a Rising Star?** Stephan Enthaler, Kathrin Junge, and Matthias Beller* Dedicated to Professor Wolfgang A. Herrmann on the occasion of his 60th birthday coupling reactions · homogeneous catalysis · iron · oxidation · reduction The development of sustainable, more efficient, and selec- tive organic synthesis is one of the fundamental research goals in chemistry. In this respect, catalysis is a key technology, since approximately 80% of all chemical and pharmaceutical products on an industrial scale are made by catalysts—even more in the case of modern processes (ca. 90%). In particular, organometallic compounds have become an established synthetic tool for both fine and bulk chemicals and several hundreds of molecular, defined pre-catalysts are commercial- ly available for chemists around the world. The reactivity and selectivity of the active catalyst are widely influenced by the choice of the central metal and by the design of surrounded ligands. During the last decades, manifold transition-metal catalysts especially based on precious metals such as palla- dium, rhodium, iridium, and ruthenium have been proven to be efficient for a large number of applications. However, the limited availability of these metals as well as their high price (Figure 1) and significant toxicity makes it desirable to search for more economical and environmentally friendly alterna- tives. A possible solution of this problem could be the increased use of catalysts based on first row transition metals, such as iron, copper, zinc, and manganese. Especially iron offers significant advantages compared with precious metals, since it is the second most abundant metal in the earth crust (4.7 wt%). Various iron salts and iron complexes are com- mercially accessible on a large scale or easy to synthesize. Furthermore, iron compounds are relatively nontoxic. In contrast to man-made precious-metal cat