Preface

Since the second edition of this book was published in 1999, thousands of papers have appeared in the literature describing all aspects of transition metals in organic synthesis including novel reactions, new catalysts, ligands, and reaction conditions and applications in synthesis of complex organic molecules. With better computational methods to probe the mechanisms of transition metal promoted reactions, a deeper understanding of the often very complex pathways for catalytic reactions has been obtained. This third edition updates the very dynamic and exponentially growing field of transition metal chemistry including literature references up to early 2008. The number of references included has almost doubled to about 1600. 

Transition metal catalyzed polymerization, synthesis of compounds of interest for material research, the use of non-conventional “green” solvents such as water, fluorous solvents, supercritical fluids, and ionic liquids, and reactions employing polymer supported reactants or catalysts have all enjoyed enormous attention. However these reactions are not mechanistically different from the more standard transformations and 

no significant differences in reactivity or selectivity compared to solution phase reactions in more standard organic solvents can be discerned. The focus of this edition is on the synthesis of small well-defined organic target molecules using more standard reaction conditions. 

Chapter 1 – Formalisms, Electron Counting, and Bonding – and Chapter 2 – Organometallic Reaction Mechanisms – dealing with the basic principles of transition metal chemistry have not been extensively updated. Chapter 3 – Synthetic Applications of Transition Metal Hydrides – details advances in homogenous hydrogenations in particular asymmetric hydrogenations, transfer hydrogenations, hydrofunctionalizations, and alkene isomerizations. Chapter 4 – Synthetic Applications of Complexes Containing Metal–Carbon s-Bonds– updates and expands on the very rich chemistry of s-metal complexes especially the synthetically important palladium catalyzed coupling reactions. Chapter 5 – Synthetic Applications of Transition Metal Carbonyl Complexes– remains the most static of all chapters and only minor revisions have been made. Chapter 6 –Synthetic Applications of Transition Metal Carbene Complexes – treats stoichiometric and catalytic reactions of metal bound carbenes. The section on metathesis processes has been significantly expanded. formation and reactivity of metal alkene complexes are described in Chapter 7 – Synthetic Applications of Transition Metal Alkene, Diene, and Dienyl Complexes. Chapter 8 – Synthetic Applications of Transition Metal Alkyne Complexes–covers alkyne complexes in organic synthesis and this chapter has been expanded with examples of the often unique reactions catalyzed by gold, silver, and platinum complexes. In Chapter 9 – Synthetic Applications of η3-Allyl Transition Metal Complexes – new examples of η3allyl chemistry in synthesis using primarily palladium catalysts. Other transition metals have emerged as competitors or complements to palladium. Finally, Chapter 10 – Synthetic Applications of Transition Metal Arene Complexes – describes the chemistry of mainly chromium, manganese, iron, and ruthenium η6complexes of arenes but also η2complexes of osmium and arenes. 

Björn C. G. Söderberg 
West Virginia University 

When it became clear that the previous version of this book was badly in need of updating and revision, I enlisted the aid of Professor Björn Söderberg, a former coworker of mine, to take on this task. I felt he was ideally suited for the job, since he had been annually reviewing the field of transition metals in organic synthesis for a number of years, a task I had done for 25 years previous to him. Although strongly based on the previous version, this revision was done almost exclusively by Professor Söderberg, with minimal help from me. Whatever added value this revision has is due to his diligence and hard work. 

Louis S. Hegedus, Professor Emeritus 
Colorado State University