Iron Catalysis

Table of Contents

1. Frontmatter

2. Catalysis by Means of Fe-Based Lewis Acids

   Juan I. Padrón, Víctor S. Martín

   Abstract

   The interest and use of iron salts as catalysts in organic chemistry has shown an exponential growth in the past years. There has been an increasing demand for environmentally friendly and sustainable chemical methods, distinguished by the low cost and environmentally benign character of the iron salts used. This chapter focuses on reactions in which iron salts produce activation on unsaturated functional groups provided by the Lewis-acid character of these salts.

3. Fe–H Complexes in Catalysis

   Hiroshi Nakazawa, Masumi Itazaki

   Abstract

   Organic syntheses catalyzed by iron complexes have attracted considerable attention because iron is an abundant, inexpensive, and environmentally benign metal. It has been documented that various iron hydride complexes play important roles in catalytic cycles such as hydrogenation, hydrosilylation, hydroboration, hydrogen generation, and element–element bond formation. This chapter summarizes the recent developments, mainly from 2000 to 2009, of iron catalysts involving hydride ligand(s) and the role of Fe–H species in catalytic cycles.

4. Fe-Catalyzed Oxidation Reactions of Olefins, Alkanes, and Alcohols: Involvement of Oxo- and Peroxo Complexes

   Kristin Schröder, Kathrin Junge, Bianca Bitterlich, Matthias Beller

   Abstract

   In this review, recent developments of iron-catalyzed oxidations of olefins (epoxidation), alkanes, arenes, and alcohols are summarized. Special focus is given on the ligand systems and the catalytic performance of the iron complexes. In addition, the mechanistic involvement of high-valent iron–oxo species is discussed.

5. Catalysis by Fe=X Complexes (X = NR, CR2)

   Chi-Ming Che, Cong-Ying Zhou, Ella Lai-Ming Wong

   Abstract

   Iron–nitrene/imido and carbene complexes are reactive chemical species capable of performing C–N and C–C bond formation, respectively. They have been widely utilized in the synthesis of natural and unnatural bioactive organic compounds and there is a growing interest in developing iron-catalyzed organic transformation reactions involving these chemical species as reaction intermediates. In the first part of this chapter, the organometallic chemistry of iron–nitrene/imido and carbene complexes including their synthesis, structures, spectroscopic properties and reactivity are presented. In the second part, a variety of iron-catalyzed nitrene and carbene transfer reactions are discussed.

6. Ferrocene and Half Sandwich Complexes as Catalysts with Iron Participation

   René Peters, Daniel F. Fischer, Sascha Jautze

   Abstract

   The unique and readily tunable electronic and spatial characteristics of ferrocenes have been widely exploited in the field of asymmetric catalysis. The ferrocene moiety is not just an innocent steric element to create a three-dimensional chiral catalyst environment. Instead, the Fe center can influence the catalytic process by electronic interaction with the catalytic site, if the latter is directly connected to the sandwich core. Of increasing importance are also half sandwich complexes in which Fe is acting as a mild Lewis acid. Like ferrocene, half sandwich complexes are often relatively robust and readily accessible. This chapter highlights recent applications of ferrocene and half sandwich complexes in which the Fe center is essential for catalytic applications.

7. Catalysis by Means of Complex Ferrates

   Markus Jegelka, Bernd Plietker

   Abstract

   Ferrates represent a class of complex iron-based anions that has a longstanding tradition in chemistry. A variety of different ferrates are accessible with their metal centers in oxidation states ranging from +III up to −II. Although they are structurally well characterized, it was only very recently that their potential as catalysts in organic reaction was explored. This chapter provides a first insight into the organometallic basics of this class of compounds, and subsequently highlights the most interesting applications of different ferrates in catalysis.

8. Backmatter