Handbook of Aqueous Solubility Data. By Samuel H. Yalkowsky and Yan He (University of Arizona). CRC Press LLC: Boca Raton FL. 2003. xii + 1496 pp. $299.95. ISBN 0-8493-1532-8. This handbook presents over 16 000 records of solubilities for more than 4000 organic compounds, including data for pharmaceuticals, pollutants, nutrients, herbicides, pesticides, agricultural, industrial, and energy-related compounds. Each compound is identified by its molecular formula, name and synonyms, molecular weight, CAS Registry Number, melting point, and boiling point, if available. A five-point rating system is also provided for each entry to assess the quality of the reporting of (1) temperature, (2) purity of solute, (3) equilibration time/agitation, (4) analysis, and (5) accuracy and/or precision. References for each entry are included, as are comments from the authors, when necessary. Three very useful indexes under the following headings complete the book: Molecular Formula; Chemical Abstracts Service Registry Number (RN); and Names and Synonyms. JA033578S 10.1021/ja033578s
Fundamentals of Molecular Catalysis. Current Methods in Inorganic Chemistry. Volume 3. Edited by Hideo Kurosawa (Osaka University) and Akio Yamamoto (Waseda University). Elsevier: Amsterdam. 2003. xiv + 522 pp. $220.00. ISBN 0-444-50921-6. According to the editors, organometallic chemistry continues to play an important and increasing role in organic synthesis and in the chemistry of polymers and materials. An in-depth understanding of the underlying principles and assumptions is necessary in order to develop and rationalize new catalytic processes. In this detailed treatise, the area of homogeneous organotransition metal catalysis is presented as a series of independent yet interconnected reaction steps that, when taken as a whole, constitute a catalytic cycle. An entire chapter is devoted to each of these reaction steps, which include ligand substitution, oxidative addition (polar and nonpolar bonds), reductive elimination, metathesis, transmetalation, insertion, and nucleophilic attack on metal-bound ligands. An exhaustive set of up-to-date references is provided as well. Each chapter is written by an author(s) well-versed in the area, and the introductory chapter serves to unite all of these steps and describe their use in practical applications. The editors state in the Introduction that the contents of the book are designed to convey the fundamental aspects of organometallic chemistry in a manner such that the reader gains the tools necessary to design, develop, and interpret a catalytic system. Toward that end, this thesis is addressed in different ways in the various chapters. The chapters on olefin metathesis Unsigned book reviews are by the Book Review Editor. 10.1021/ja033578s CCC: $25.00 © 2003 American Chemical Society
and 1,2-insertion provide very useful mechanistic and theoretical descriptions that provide insight into the area and are useful to anyone trying to develop a conceptual understanding of the topics. The depth of information presented in these chapters is not found in textbooks on organometallic chemistry and is difficult to glean from the large body of literature available on the topic. In contrast, the chapters on activation of polar bonds and transmetalation are basically catalogs of reactions. Only a moderate amount of information is presented in terms of mechanistic understanding, and, as such, these chapters come off more as detailed literature searches than a review of basic information. Nonetheless, they do contain more information on their subject than most reviews and include topics rarely covered in great detail in textbooks. The remaining chapters fall somewhere between these two styles. Depending on the reader’s needs, this spectrum of presentation styles may diminish the usefulness of the book. Overall, this volume provides excellent coverage of nearly every aspect of organometallic chemistry and is presented in a manner that makes it easy to find information on many subjects. I believe a scientist well-versed in the field will still find useful information here; likewise, the scientist interested in organometallic chemistry for his or her own applications (e.g., a synthetic organic chemist) may also find this book useful. Although this book is a timely addition to the organometallic literature, at $220, it is very expensive for an individual to purchase. It clearly merits addition to a university or industrial library, however. David Tellers, Merck & Co., Inc. JA033574N 10.1021/ja033574n
Hydrocarbon Chemistry, Second Edition. By George A. Olah (Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles) and AÄ rpa´ d Molna´ r (University of Szeged, Hungary). J. Wiley & Sons, Inc.: Hoboken, NJ. 2003. xxiv + 871 pp. $150.00. ISBN 0-471-41782-3. The second edition of this classic treatise by Olah and Molna´r brings the reader up-to-date on developments in the organic chemistry of hydrocarbons from 1994, when the first edition was published, through 2001. The presentation follows the general format of the first edition, in which each hydrocarbon transformation, including isomerization, addition, alkylation, carbonylation, acylation, oxidation/oxygenation, heterosubstitution, reduction/hydrogenation, metathesis, and oligo/polymerization, is discussed from the point of view of reactivity, selectivity, stereochemistry, and mechanisms, together with industrial (petrochemical) applications of various alkanes, olefins/acetylenes, and arenes. Each subject is extensively annotated with a comprehensive subject index, which will enable the interested reader to quickly gain valuable access to the J. AM. CHEM. SOC. 2003, 125, 13619-13622
9
13619
BOOK REVIEWS
current literature on a particular hydrocarbon transformation. The inclusion of the latest emerging technologies of combinatorial synthesis, fluorous catalysis, solvent-free/green chemistry, and the utilization of carbon dioxide largely within the last seven years also accounts for the substantial increase in the number of pages as compared to the first edition and ensures that Hydrocarbon Chemistry will be a continuing first-source of vital information for this core component of contemporary organic chemistry.
This book is well written and can serve as a textbook for a graduate level course in the area of electron transfer and energy transfer processes for the development of modern optoelectronic devices; it can also be used as a source of leading references for the practitioner in this ever-evolving area of research. In summary, I highly recommend this book and strongly believe that it will have great practical utility for students and practitioners in the areas of nanoscience, nanotechnology, electron transfer, and energy transfer processes. Rajendra Rathore, Marquette UniVersity
Jay K. Kochi, UniVersity of Houston JA033567Z
JA033539G 10.1021/ja033539g
10.1021/ja033567z
Interfacial Supramolecular Assemblies. By Johannes G. Vos, Robert J. Forster (Dublin University), and Tia E. Keyes (Dublin Institute of Technology). John Wiley & Sons, Ltd.: Chichester. 2003. xi + 317 pp. $195.00. ISBN 0-471-49071-7. The design and synthesis of novel supramolecular assemblies of suitably tailored (electroactive) organic, organometallic, and biomolecules are being developed at an unabated pace. Electron transfer and energy transfer form the fundamental basis for the (photo)conductivity, ferromagnetism, and nonlinear optical response in various assembled materials and thus undoubtedly will play a critical role in the creation of modern interfacial supramolecular assemblies in the emerging area of molecular electronics and nanotechnology. Accordingly, the time is ripe for a book to emerge that utilizes a simplified approach to describe the self-assembly of these electroactive materials on a molecular level on various surfaces, and this contribution does just that. It also includes discussion of the characterization of these materials and techniques for exploring their optoelectronic properties, and at the same time allows the reader to develop a fundamental understanding of the processes of electron and energy transfer in such assemblies. In the introductory chapters, the book establishes the theoretical background for electron transfer and energy transfer processes in an understandable way and also includes leading references for more advanced readers. A brief description of various modern techniques, for example, scanning probe microscopy, scanning electrochemical microscopy, various voltammetric methods, luminescence spectroscopy, Raman spectroscopy, and time-resolved spectroscopic techniques, etc., for the characterization of interfacial supramolecular assemblies follows with appropriate references. Later chapters include discussions of the fabrication of self-assembled monolayers, thin polymerfilms,biomimeticassemblies,etc.,onvarioussurfacessoften with examples from recent literaturesas well as electron and energy transfer dynamics on the molecular level in these assembled structures. The final chapters cover the hybrid systems in which semiconductor surfaces such as TiO2 are modified with various organic and organometallic derivatives for the preparation of nanoscale molecular devices. Directions for future research in such areas as diverse as solar energy storage, nanotechnology, and biosystems and material science using interfacial supramolecular assemblies are also provided. Most of the chapters in the book are presented in a systematic fashion and include leading references that are fairly up-to-date. 13620 J. AM. CHEM. SOC.
9
VOL. 125, NO. 44, 2003
Synthetic Methods in Step-Growth Polymers. Edited by Martin E. Rogers (Luna Innovations, Blacksburg, VA) and Timothy E. Long (Virginia Tech). J. Wiley and Sons, Inc.: Hoboken. 2003. xii + 606 pp. $129.95. ISBN 0-471-38769-X. This is an up-to-date review of synthetic methods in stepgrowth polymers. Although from a scientific standpoint these polymers are a relatively mature subset in the field, this book serves the very valuable function of summarizing the present status of the various synthetic approaches to them. The chapters are written by experts known worldwide with respect to the topics at hand. Following an introduction to the title subject, the families of polymers reviewed include polyesters, polyamides, polyurethanes, polyureas, polyimides, and other hightemperature polymers, poly(arylene ether)s, phenolic resins, and networks. Two significant chapters cover nontraditional stepgrowth polymerization-ADMET and transition metal coupling, and the final chapter deals with the important subject of depolymerization and recycling. The inclusion of these last three chapters reflects the current active interest in this area. Each of the chapters has many up-to-date references, making it easy for the reader who has a specific interest to research the topic further. Useful in many, but not all, of the chapters are sections dealing with analytical methods applicable to these polymer systems as well as specific examples of detailed synthetic procedures. This book definitely fills a need for practicing polymer chemists and is the kind of reference that they should have at their desk. It also would be a useful textbook for a course on polymer synthesis. The editors have accomplished their goal of producing a textbook that will “... serve as a long-standing resource for fundamental concepts in step-growth polymerization processes.” Eli M. Pearce, Polytechnic UniVersity JA033557Y 10.1021/ja033557y
The Chemistry of Organic Germanium, Tin and Lead Compounds, Volume 2. Parts 1-2. Edited by Zvi Rappoport (The Hebrew University, Jerusalem). John Wiley & Sons, Ltd.: Chichester. 2002. xl + 1912 pp. $1510.00. ISBN 0-471-49738-X. K. M. Mackey, in the first volume of this work, published in 1995, stated that there is “a rich chemistry of each individual
BOOK REVIEWS
element, a subtly varying relationship between them, and sufficient unexpected and at present unique behavior to indicate that further development will be exciting and complex.” The present volume contains many chapters on topics not included in the 1995 edition, with updates to the literature up to 2001. Coverage in this volume is considerably enhanced over Volume 1, both in the topics chosen and in the expertise of the authors; that is, most of the current senior authors have been major contributors to the areas they are reviewing. The first chapter, by Voronkov and Abzaeva, is an historical account of the evolution of organogermanium, -tin, and -lead chemistry, and its 130 pages are a catalog of early contributions to the field. Rappoport in his forward pointed out that articles in Russian were previously not available to non-Russian readers and that this lack has now been remedied through citations in Chemical Abstracts and other sources. There are 1412 references in the first chapter, although coverage is somewhat sparse after 1970 and some more recent areas receive scant attention. In Chapter 2, Voronkov and Egorochkin describe the similarities and differences of organic compounds of Ge, Sn, and Pb and present a point of view based largely on Russian work that is quite distinctive. The picture presented in assigning a prominent role to d-orbitals in covalent bonding differs somewhat from the models employed by many main-group chemists. Regrettably, the scarcity of references from the past decade has led the authors to overlook the existence of persistent molecules containing divalent heavy atoms in group 14. This chapter is followed by Ganzer, Hartmann, and Frenking’s clear summary of the modern theoretical methods employed using organic germanium, tin, and lead compounds. It is upto-date, as are all succeeding chapters. Combined experimentaltheoretical investigations are well represented and signal a wave of the future for this type of approach. In the next three chapters, respectively, Klinkhammer reviews recent advances in structural chemistry, concentrating on divalent and multiply bonded compounds, Riveros and Takashima offer a succinct description of the mass spectrometry and gas-phase chemistry of Ge, Sn, and Pb species, and Marsmann and Uhlig cover advances in Ge, Sn, and Pb NMR spectroscopy, a topic that received scant attention in Volume 1. This last chapter includes tables of 73Ge, 119Sn, and 207Pb NMR data culled from 443 references dating from 1995 to 2000. In Chapter 7, Riena¨cker and Klapo¨tke review the acidity, complexing, basicity, and H-bonding of organic Ge, Sn, and Pb compounds, updating the 1995 contribution by the latter author. The focus here is on synthesis, reactions, and molecular structure rather than on mechanisms, spectroscopic properties, and applications. The succeeding chapter by Charton, entitled “Structural Effects on Germanium, Tin and Lead Compounds”, updates his 1995 contribution. A proponent of structure-property quantitative relationships, Charton employs electrical effect substituent constants, steric effect parameters, and intermolecular force substituent constants to correlate and predict a variety of properties. Agreement between observed and calculated values is often quite good, so these relationships have some predictive value, but their claimed explicatory function has not, in my view, been demonstrated. A distinctive contribution is Chapter 9, “Radical Reaction Mechanisms of and at Organic Germanium, Tin and Lead” by
Taraban, Volkova, Kruppa, and Leshina. The use of chemically induced dynamic nuclear polarization signals and magnetic field effects on product ratios to elucidate reaction mechanisms is described. Even if a few of the mechanistic conclusions presented are not entirely convincing, the authors have succeeded in their goal of attracting the attention of the organometallic community to the options offered by “spin chemistry” methods. Zharov and Michl summarize the investigation of R3M+ cations (M ) Ge, Sn, Pb) in the next chapter. Despite considerable recent progress, the authors point out that the characterization of these cations appears to be even more challenging than that of silyl cations due to the weaker and longer bonds to the carbon atom in the heavier examples of the species, R3M+. In Chapter 11, Riviere, Castel, and Riviere-Baudet discuss the preparation, spectroscopy, structure, and reactivity of alkaliand alkaline earth metal-14 compounds, and in Chapter 12, Boganov, Egorov, Faustov, and Nefedov review spectroscopic and theoretical studies of divalent Ge, Sn, and Pb compounds, including the experiments that produced them and their interpretation. In the latter chapter, the characterization of weak interactions of heavier carbene analogues in solution, their preparation in triplet ground electronic states, the determination of their singlet-triplet splittings, the reactivity of their triplet states, and the development of new precursors for these analogues of carbenes and silylenes are cited as important problems remaining to be solved. Tokitoh and Okazaki review multiply bonded Ge, Sn, and Pb compounds in Chapter 13. The lack of heavy ketones R2MdO (M ) Ge, Sn, Pb) and “heavy” aromatics, that is, benzene rings containing from one to six Ge, Sn, or Pb atoms, is noted by the authors. In the following chapter, Lee and Sekiguchi offer scope for future research on unsaturated threemembered rings of the heavier group 14 elements, since virtually none of the mechanisms for the formation or reactions of these molecules is known. Cage compounds of the heavier group 14 elements are covered in Chapter 15, which is written by these same two authors. The variation in the strain energies in the series of C, Si, Ge, and Sn tetrahedranes is quite different from that of the corresponding cubanes and prismanes and can be rationalized by the decrease in hybridization for the heavier elements. Chapter 16 is a long contribution of 276 pages, 1281 references, and 593 numbered structures in which Baukov and Tandura summarize a burgeoning field: the synthesis, structure, and reactions of hypervalent Ge, Sn, and Pb compounds. In Chapter 17, Sharma, Haiduc, and Pannell discuss transition metal complexes of Ge, Sn, and Pb, focusing on their synthesis and characterization and including a section on the use of 207Pb NMR spectroscopy to study transition metal-lead bonds in solution. Fouquet has authored a tightly constructed essay on synthetic applications of organic Ge, Sn, and Pb compounds in the next chapter, although the focus here is almost entirely on the chemistry of tin compounds. Some of the topics covered include nucleophilic addition, metal-catalyzed coupling reactions, free radical reactions, transmetalations, and substitution reactions. Chapter 19 on the synthetic uses of R3MH (M ) Ge, Sn, Pb) by Carland and Schiesser is a crisp review of the free-radical chemistry of tin-based chain-carrying reagents, along with a bit J. AM. CHEM. SOC.
9
VOL. 125, NO. 44, 2003 13621
BOOK REVIEWS
of germanium chemistry. The vast majority of the 865 references are from the 1990s, with many from 2000. In the following chapter, Kolesnikov, Tandura, and Nefedov briefly describe trichlorogermane as a new superacid; its Ho value is estimated to be -13.0, similar to that of perchloric acid! Chapter 21 by Long and Pryce covers the photochemistry of the organometallic compounds of Ge, Sn, and Pb. The authors note that the photochemistry of the heavier group 14 organometallic compounds is significantly different from that of their organosilicon cousins, but the coverage of the topic seems a bit thin. In contrast, the next chapter by Jurkschat and Mehring on organometallic polymers of Ge, Sn, and Pb is a substantial overview of materials prepared largely during the past half decade and includes synthetic routes, structures, and structureproperty relationships. The remaining two chapters are updates of contributions to the 1995 volume on the biological activities of organogermanium (by Lukevics and Ignatovich) and organotin and organolead compounds (by Lukevics and Pudova).
13622 J. AM. CHEM. SOC.
9
VOL. 125, NO. 44, 2003
All in all, this volume presents a coherent picture of the chemistry of organogermanium, -tin, and -lead compounds, whereas the 1995 work is more fragmentary and can now be regarded as a “special topics” supplement to its 2002 successor. One feature that would have enhanced the value of these reviews would be if more of the authors had compared the behavior of these compounds with the corresponding organosilicons. Nonetheless, I believe chemistry libraries of the first rank should acquire this volume, despite a cost so high that private purchase is precluded. Given the price and the fact that these books will only be found in libraries where they will receive rough use, it is aggravating that the sturdy cloth covers of the 1995 volume have been replaced by flimsy paper-covered boards. Peter P. Gaspar, Washington UniVersity JA033558Q 10.1021/ja033558q
