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Organometallics 2011, 30, 196–198 DOI: 10.1021/om101126k
New Organometallic Textbook Reviews Oscar Navarro, David A. Vicic,* and Craig Jensen Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822, United States
The Organometallic Chemistry of the Transition Metals, 5th ed. Robert H. Crabtree (Yale University, USA). Wiley: Hoboken, NJ, USA. 2009. ISBN 978-0-470-25762-3. Most of the organometallic chemists formed in the last 20 years (and many, many others) have a copy of any of the previous editions of this textbook;including me. Concise descriptions of the concepts and updated examples in the literature available at the time of edition, together with a reasonable price, have made The Organometallic Chemistry of the Transition Metals the book of choice of many instructors and researchers in a variety of fields through these years. The fifth edition of The Organometallic Chemistry of the Transition Metals takes the place of the previous edition released in 2005. The distribution of the chapters remains the same as that in the fourth edition: introduction (Chapter 1), general properties of organometallic complexes (Chapter 2), types of ligands and bonding (Chapters 3-5 and 11), mechanisms (Chapters 6-8), applications (Chapters 9, 12, and 14), physical methods (Chapter 10), clusters and metal-metal bonds (Chapter 13), paramagnetic complexes (Chapter 15), and bioorganometallic chemistry (Chapter 16). The reader will notice from the first chapter that the major improvement when compared to the fourth edition is the use of newer references at the end of the chapters to illustrate or support concepts. Unfortunately, this cannot be said about the list of “Useful Texts on Allied Topics” at the end of the book, which has barely changed regardless of many excellent books that have appeared in the last half decade. Through the book, the author has inserted paragraphs in some chapters with new topics and developments such as the sdn model or single-molecule imaging. The contents of the chapters related to ligands and mechanisms remain pretty much identical in terms of contents, explanations, and examples. It is surprising that the author, being an authority on NHCs (N-heterocyclic carbenes), did not update the related section more than to reference one of his articles on chelating NHCs, considering all the studies regarding electronic and steric effects available in the literature. No or minimal changes can be found either in the chapters dedicated to applications of organometallic chemistry, paramagnetic complexes, or bioorganometallic chemistry. On the other hand, the author has removed the sections regarding synthesis and reactions of metal clusters in Chapter 13. To my delight, the chapter devoted to applications to organic synthesis has been completely rewritten, including very recent examples in the literature, and so were the corresponding end-of-chapter problems. About a half-dozen new problems are also scattered within the other 15 chapters. One of the appeals of this book when considering it for an undergraduate or graduate course is the inclusion of these problems and, probably just as important, solutions to them at the end of the book. This is not, though, an exclusive feature of this book (see the other reviews in this journal issue). pubs.acs.org/Organometallics
Published on Web 12/31/2010
In summary, this fifth edition sticks to the model and standards set by the author a long time ago that made it a very successful book. Readers that did not find previous editions of this book suitable for their needs (teaching or reference) should not expect that this new edition will have something that changes their mind. At the same time, that same model guarantees that it will still be one of the primary choices of the next generation of organometallic chemists and readers with interests in organometallic chemistry.
Oscar Navarro Organotransition Metal Chemistry: From Bonding to Catalysis. John Hartwig (University of Illinois, Urbana-Champaign). University Science Books: Sausalito, CA 2010. ISBN 978-1891389-53-5. The 1127-page book by Hartwig with large, densely packed pages represents a thoroughly updated version of the 1987 classic Principles and Applications of Organotransition Metal Chemistry, by Collman, Hegedus, Norton, and Fink. As more than 20 years have passed since the original edition of the book, such a complete overhaul was needed, and Hartwig himself notes that “every chapter, section, paragraph, sentence, and, yes, title are revised from the book published in 1987.” To accomplish this massive overhaul of a landmark text, Hartwig recruited a number of experts in the field, and together they constructed what is sure to be considered a classic in its own right for years to come. Chapter 1 lays out in a logical order the basic fundamentals needed to make sense of the vast array of metals, oxidation states, valencies, and ligands found in the organometallic field. Formalisms regarding electron counting are clearly described, including updated notes regarding possible pitfalls when dealing with bridging hydrides and metal-metal bonds. However, the authors still describe the linear nitrosyl ligand as retaining a 1þ charge in an actual complex, retaining the outdated M-rNtOþ description, even though it is becoming clearer that multiply bonded resonance structures of the types MtNþ-O- and MþdN-O-are actually preferred. Chapters 2-4 then go on to further describe structure and bonding in relation to the ligands that metals possess, and whether or not these ligands are dative or anionic. The dative section describes the usual CO, olefin, and phosphine complexes, with heavily updated sections on metals bearing N-heterocyclic carbene ligands and σ complexes (recall that the first metal-dihydrogen complex was only discovered 3 years before the publication of Principles and Applications of Organotransition Metal Chemistry). Chapters 5-12 cover fundamental reactions in organometallic chemistry such as ligand substitutions, oxidative additions and reductive eliminations, migratory insertions/eliminations, and nucleophilic/electrophilic attack on coordinated ligands. A unique departure from the original text is that a separate chapter (Chapter 13) is dedicated to metal-ligand multiple bonds. This is appropriate, as new advances in rhodium r 2010 American Chemical Society
Book Reviews
carbene chemistry, metathesis reactions, atom transfers, and inorganic/organometallic synthesis have led to a rich field of chemistry involving multiply bonded metals. Another unique addition to the book is a stand-alone chapter (Chapter 14, written with Pat Walsh) that provides a pedagogically useful introduction to the principles of catalysis. This chapter provides a sound launching pad for the remainder of the text, which covers important catalytic reactions involving metal-carbon bonds. These reactions include metal-catalyzed hydrogenations, hydrofunctionalization and oxidative functionalization of olefins, catalytic carbonylation, catalytic C-H functionalization, coupling reactions, allylic substitutions, metathesis, and polymerization/oligomerization reactions. Perhaps the two most impressive and distinguishing chapters in the Hartwig text are the 90-page chapter on homogeneous hydrogenation (Chapter 15) and the 88-page Chapter 19, dedicated to transition-metal-catalyzed coupling reactions. Chapter 15 has an exceptionally thorough section on asymmetric and transfer hydrogenations. The large expansion of this section is quite telling of the scientific progress that has been made since the publication of Principles and Applications of Organotransition Metal Chemistry, considering the original authors of that book stated “only a restricted class of olefinic substrates like MAC are likely to afford high stereoselectivity” and “a systematic search for other asymmetric hydrogenation catalysts seems hopeless.” Other topics discussed in Chapter 15 include mechanisms of hydrogenations, ligand effects, hydrogenation of alkynes and conjugated dienes, hydrogenation of arenes and heteroarenes, and hydrogenation of carboxylic acid derivatives. There is no doubt the expertise of the author in the field helped him construct the chapter in metal-catalyzed coupling reactions (Chapter 19), which is unmatched by any other comprehensive organometallic textbook. The chapter begins by describing classic reactions, some of which helped define the area of organometallic chemistry that led to the 2010 Nobel Prize. The chapter then takes a closer look into the salient features of different nucleophiles, ligand electronic effects, stereoselective reactions, and mechanisms of cross-coupling reactions. The chapter concludes with an in-depth survey of reactions of current interest such as carbon-heteroatom bond forming reactions, new advances in copper-catalyzed reactions, and direct arylations. Organotransition Metal Chemistry: From Bonding to Catalysis is a text that seems at place at major research universities for students and departments with serious interests in long-term organometallic pursuits. The lack of any practice problems and overall size may deter small undergraduate programs from using this text as a teaching tool, especially with a number of smaller texts on the market (see the other reviews in this journal issue). However, a plus side to the book’s extensiveness is that it could be used to cover a twosemester course on organometallic chemistry, which would make the cost of the text more attractive to starving graduate students. A logical division would be to include Chapters 1-13 in a first-semester course to cover the fundamentals of structure, bonding, and reactivity and then use Chapters 14-22 in a second-semester course to cover catalytic applications. While practitioners can certainly peruse the book and pick out omissions, both in subject area and in cited examples, the text as a whole represents a remarkable update of the last 20 years. Many fields of science have a resource book that is always within arm’s reach of the experts in that field. This
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new text by Hartwig will be that book for current and future organometallic chemists.
David A. Vicic Organometallic Chemistry, 2nd ed. Gary O. Spessard and Gary L. Miessler. Oxford University Press: New York, 2010. ISBN 978-0-19-533099. Since it first appeared in 1997, Organometallic Chemistry by Spessard and Miessler has earned a reputation as a highly readable, thorough text. The subject mater is present in a style that easily comprehended by graduate or undergraduate students with a BS level understanding of organic and inorganic chemistry. The book’s approach is to first establish a structurebonding foundation that is based on molecular orbital theory. Once this background is established, the authors present indepth surveys of π and σ ligands. This sets the stage for a methodical coverage of the full range of reactions of organotransition-metal complexes and many of the practical applications of this chemistry. This smooth flow is essentially unchanged in the new, second edition of the book. However, some significant improvements have been made, including the addition of many more problems at the end of the chapters. The added exercises have a widely varied level of difficulty and focus and therefore allow the instructor much more flexibility in the selection of assigned problems. Another major improvement is that the chapter on the applications to organic synthesis and the now entire chapter on metathesis and polymerization reactions have been expanded and updated. As a result, this text would be well-suited for a course in which applications to organic synthesis are to be heavily emphasized. This edition has also been expanded to include examples of green chemistry based on organometallic catalysts that are likely to be of great interest to a contemporary student audience. The text in general is excellent. However, it does have several relatively minor flaws. The coverage of the spectroscopic characterization of organometallic compounds is insufficient and poorly organized. Most notably, the discussion of dynamic phenomena in NMR spectrometry is far too brief and the coverage of infrared spectroscopy is limited to only carbonyls and nitrosyls. It is also difficult to locate specific text on spectroscopic characterization, as it is sprinkled throughout Chapters 4-6. It could also be questioned whether the “more extensive treatment of the industrial applications” represents an overall improvement in the second edition. In some cases, such as the coverage of the ibuprofen synthesis, the additions are truly excellent. However, there are several examples of overkill where the lengthy discussion is more suited to a review article. The most poignant example of this is the 8 pages devoted to the hydroformylation reaction (which is strangely presented before simple hydrogenation). The pageafter-page coverage of the history and details of the evolution of the industrial processes fails to provide students with a sharp focus on the basic mechanism and important features of the currently utilized industrial reaction. Finally, the coverage of some of the topics in the applications to organic synthesis chapter, such as asymmetric oxidations, is too brief and would require supplementation by the instructor. In summary, the second edition of Organometallic Chemistry is a highly readable text that is appropriate for a gardenvariety course in organometallic chemistry for an audience of first-year graduate and/or upper division undergraduate
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students. Students will no doubt find the book to be highly comprehensible and will be served well by the excellent problem sets. Instructors wishing to emphasize applications to organic synthesis should find the expanded Chapters 11 and 12 (and even Chapter 9) in the new addition to be much to their liking. Anyone teaching a course in organometallic chemistry should seriously consider adoption of this text.
Craig Jensen Basic Organometallic Chemistry: Concepts Syntheses and Applications of Transition Metals, International Edition. B. D. Gupta and A. J. Elias. Universities Press and CRC International: Hyderabad, India, 2010. ISBN: 978-14398-4968-2. The text Basic Organometallic Chemistry is a newcomer to the market this year and has as its objective “to inculcate interest in understanding transition metal organometallic chemistry in the beginners of organometallic, inorganic and organic chemistry as well as research scholars in academia and industry.” The book is easy to read, and with many descriptive sections will be accessible to beginning graduate and higher level undergraduate students. Students will also appreciate the effort that was made to provide many end-ofthe-chapter questions, complete with answers at the back of the book. What will also be quite appealing to students are the nice sections in Chapter 1 on the brief history of the field and the importance of organometallic compounds as reagents, additives, and catalysts. However, the attempts of the authors to untangle complex chemistry and formalisms do not always hit the mark. For
instance, the chapter on the 18-electron rule was much too oversimplified and in need of a molecular orbital analysis to describe why sub-18-electron square-planar and tetrahedral complexes are prevalent in the literature. More details about the treatment of bridging hydrides and the pitfalls that could be encountered when counting electrons would also help strengthen this chapter. Other simple things could have greatly impacted the splash that this first edition will make. The chemical drawings are not always clean, even to the point that they become a distraction. A better molecular orbital description of carbon monoxide, explaining why metals bind to the carbon atom, is needed. N-heterocyclic carbene metal complexes are drawn in different ways throughout the text, which may confuse beginning students. Transition-state diagrams of β-hydride elimination and alkene insertion are drawn incorrectly. The coverage of oxidative addition and reductive elimination is much too short and will require supplementation by instructors. Nevertheless, the descriptive approach to organometallic chemistry has its place, and the job that Gupta and Elias have done in putting together this first edition is commendable. The book is rife with interesting little tidbits and anecdotes about discoveries, practical uses of complexes, and case studies. Separate stand-alone chapters on metal clusters, ferrocene: structure, bonding, and reactions, and organometallic polymers are, as far as I can tell, unique to this text and may be of interest to instructors who practice in these fields. Overall, the book will provide some serious competition to texts already in print, and a more careful upgrade may even transform this into the preeminent text for undergraduate institutions.
David A. Vicic
