Organometallics, Vol. 3, No. 11, 1984 1775
Book Reviews
Book Reviews Comprehensive Organometallic Chemistry. The Synthesis, Reactions and Structures of Organometallic Compounds. Volume 7. Edited by G. Wilkinson, F. G. A. Stone, and E. W. Abel. Pergamon Press, Oxford. 1982. xii + 729 pages. Volumes 1 and 2 of “ComprehensiveOrganometallicChemistry” dealt with the organic chemistry of the main-group metals and metalloids as well as of the elements of periodic groups 1B and 2B. Preparative aspects, structure, and bonding as well as reactivity were discussed. However, the coverage was not complete in that in most cases little if anything was reported about the application of the organometallic derivatives of these elements in organic synthesis. This was deliberate, for a separate volume of this series is devoted in its entirety to the applications of main-group organometallic reagents in organic synthesis. This was an important aspect of main-group organometallic chemistry right from its beginnings in the 185Os, Frankland having devoted some efforts to the study of the reactions of the then newly discovered organozincs with organic carbonyl compounds. With the advent of the Grignard reagents a t the turn of the century, organomagnesium compounds became an important weapon in the arsenal of the synthetic organic chemist. In the 16 chapters of the present volume we have a fairly up-to-date exposition of main-group organometallic chemistry as it relates to synthetic organic chemistry. On looking over the space allocated to various topics, one gets the feeling that organoboron chemistry is a bit overemphasized with ita 253 pages. In contrast, organoalkali and organomagnesium chemistry together make do with a chapter of only 111 pages; organminc, -mercury,and -copper reagents are covered in a chapter of only 69 pages. Organotin compounds are not mentioned at all. This is difficult to understand in view of their proven utility in organic synthesis in recent years. Nonetheless, this is a worthwhile book, one that the organic chemists will f i d most helpful not only for the chemistry it brings but also for the many references to the original and review literature which are cited. The author of the group 1A/2A chapter, B. J. Wakefield, previously has written an excellent book on organolithium chemistry in which the synthetic organic aspects were covered in detail, and his chapter in the present book gives a nice summary of RLi and RMgX chemistry as applied to problems of organic synthesis. The organoboron section that follows is led off by an introductory survey by H. C. Brown and is continued by M. Zaidlewicz with a very thorough discussion of all aspecta of the hydroboration reaction. Full details on organoborane reactivity, especially as applied to organic synthesis, follow in several chapters by E.-I. Negishi. These are organized according to type of organoborane. Organoboranesare versatile, easy-bprepare, in part, commercially available intermediates, and the organic chemist will find much in these chapters that can help him toward his goals in synthesis. While organoboranes have in the main been confined to the research laboratory in their various organic applications, organoaluminums, the subject of the next chapter by J. R. Zietz, Jr., G. C. Robinson, and K. L. Lindsay, have become large-scale commercial chemicals, thanks to the chain growth reaction and Ziegler-Natta catalysis. On the other hand, they have not caught on in the research laboratory the way boranes have. Nonetheless, as this detailed chapter makes clear, there is much potentially useful organoaluminumchemistry that the synthetic chemist could apply with advantage-provided he is not deterred by the safety and handling problems associated with organoaluminum compounds as described by the authors. Modern organothallium methodology as applied to problems of organic synthesis was developed in large part by A. McKillop and E. C. Taylor and their respective research groups. McKillop and Taylor have provided an excellent summary of this area with the focus on the oxythallation of olefins and the thallation of
aromatic systems and the varied synthetic consequences of these reactions. Group 4 is represented only by the long (145 page) chapter on organosilicon compounds by P. D. Magnus, T. Sarkar, and S. Djuric. The material presented is organized according to silane type: allyl-, vinyl-, alkynyl- (and propargyl- and allenyl-), and benzylsilanes; silyl enol ethers, silanes with Si heteroelement functionality, including silyl metallics; silyl hydrides, ylides, and acyls, with separate sections on Me3SiI,Me3SiCN,and Me3SiN3 Magnus and his coauthors have done a fine job of summarizing the important contributions of organosilicon chemistry to organic synthesis. The last chapter, by W. Carruthers, which covers the organic compounds of zinc, cadmium and mercury and of copper, silver and gold, is perhaps the least satisfactory. In the zinc and cadmium sections the author has virtually ignored the significant French contributionsto organic synthesis as assisted by the organic derivatives of these metals. In the mercury section the mercuration of aromatics and the use of arylmercurialsin synthesis find no mention. Neither are Giese’s interesting free radical additons as effected by the reaction of diverse RHgX with NaBH4and other hydrides in the presence of organic radical acceptor molecules included. The section on organocopper compounds and intermediates in organic synthesis is much better. One may venture to predict that Volume 7 will be one which will find much use since its subject matter will be of interest and importance both to the organometallic and the organic chemist. Dietmar Seyferth, Massachusetts Institute of Technology Organometallic Chemistry Reviews; Annual Surveys: Silicon-Lead. Volume 14 of the Journal of Organometallic Chemistry Library. Edited by R. B. King and J. P. Oliver. Elsevier, Amsterdam. 1984. 536 pages. $152.00. The lateat volume of the Journal of Organometallic Chemistry Library brings four silicon annual surveys [“Silafunctional Compounds: Synthesis and Reactivity” for 1981 (531 references) and 1982 (506 references) by J. Y. Corey; “The SiliconCarbon Bond” for 1981 (466 references) by G. L. Larson; “Organosilicon Reaction Mechanisms” (290 references) by F. K. Cartledge] and the 1981 organolead survey (169 references) by J. Wolters and D. de Vos. Although the 1981 surveys are rather late in appearing, they are nonetheless welcome. Organosilicon chemistry is such an active field, with so many papers appearing each year which deal with the various aspects of this important area that it has become almost impossible to keep up with ita literature. Thus such comprehensive surveys are a great help to the organosilicon chemist. All the chapters in this book are excellently done. They are well organized, and the material is clearly presented by means of text and many equations, schemes, and tables. The many references that are given will be invaluable to the reader who wishes to survey a given aspect more deeply. The authors of the various surveys appear to have been quite thorough; at any rate, those areas with which your reviewer is familiar are well done. This book is well and attractively produced. It is impressive in every way, including price. Most of those who will wish to sample its wares will have to do so in their library. Dietmar Seyferth, Massachusetts Institute of Technology Gmelin Handbook of Inorganic Chemistry. 8th Edition. Ti. Organotitanium Compounds. Part 3. Mononuclear Compounds 3. U. Thewalt, volume author. A. Slawisch, volume editor. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin/Heidelberg/New York. 1984. ix + 268 pages. DM 880, $341.50. The bis(~5-cyclopentadienyl)titanium halides are easily pre-
1776 Organometallics, Vol. 3, No. 11, 1984 pared, and their reaction chemistry has been studied extensively. As a result, many (#-CsH5)zTi” and -Tim derivatives have been prepared and characterized. The present volume of the Gmelin organotitaniumseries continues the coverage of such compounds. The books start out with Cp2TiWoxy derivatives, alkoxides, aryl oxides, and carboxylates in the main. These are followed by Cp2TiWcompounds with sulfur, selenium, and tellurium substituents of various kinds, with nitrogen and phosphorus substituents, and with group 4 R8M Substituents. Also covered are bis(cyclopentadieny1)titanium compounds with two different substituents, principally of type Cp2TiX(OR),those with chelating ligands (e.g., 8-diketonates, dithiocarbamates, etc.). A major part of the book is devoted to Cp2Ticompounds that also contain one or two T i 4 u-bonded organic groups (alkyl, aryl, acyl, etc.). These include the simple CpzTiR and CpzTiRztypes as well as more complicated systems. The literature, which includes original research papers, reviews and monographs, patents, theses, and conference reports, has been covered exhaustively through the end of 1979,partially even past this date. The listing of review articles and books dealing wholly or in part with organotitanium chemistry, which was begun in Part 1 and continued in Part 2, is updated through the end of 1980. The reader will find information and references relating to the preparation, physical and spectroscopic properties, structures, and the reactions of the compounds covered. As is the case in all Gmelin volumes, this information is presented in a well-organized and systematic manner with many equations, formulas, figures, and tables of data: another fine contribution from the Gmelin Institute. Dietmar Seyferth, Massachusetts Institute of Technology
Organic Reactions. Volume 31. W. G. Dauben, Editor in Chief. Wiley, New York. 1984. vii 376 pages. $44.50.
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Volume 31 of Organic Reactions continues the fine tradition of its prececessors. This.volume,contains a single chapter titled “Addition and Substitution Reactions of Nitrile-Stabilized Carbanions”, written by S. Arseniyadis, K. S. Kyler, and D. S. Watt. This chapter thoroughly reviews the generation of nitrile-stabilized carbanions and their subsequent reactions with electrophiles. As is standard for contributions to Organic Reactions, the text is followed by an extensive tabulation (273 pages) of specific examples. The literature citations are extensive, covering references through February of 1982. Included in this chapter are sections on the generation and reactions of carbanions derived from alkyl- and aryl-substituted nitriles, and 8,yunsaturated nitriles, and protected cyanohydrins as well as nitriles bearing sulfur, dialkylamino, and halogen substituents. Particular attention is focused on the scope and limitations of these reactions with good attention to mechanistic deta i1.
Book Reviews Several features make this review particularly useful: (1)It contains a detailed table of contents. (2) Within the chapter, reactions are logically grouped, first with respect to the variety of the nitrilestabilized carbanion (sixseparate sections) and within these sections with respect to the electrophile. This makes finding information about a specific reaction extremely easy. (3) As in previous chapters in this series, representative experimental procedures are included. In summary,Professor Watt and coauthors have produced an excellent addition to this valuable series, meeting its high standards by producing a well-written, comprehensive review. This volume should prove to be a useful addition to the institutional and personal library alike. Stephen L. Buchwald, Massachusetts Institute of Technology
Mechanisms of Inorganic and Organometallic Reactions. Edited by M. V. Twigg. Plenum Press, New York. Volume 1. 1983. 373 pp. $49.50. Volume 2. 1984. 453 pp. $59.50. These volumes are the first in a new series that is the clear successor to the now-defunct Inorganic Reaction Mechanisms volumes in the Specialist Periodical Reports (Royal Society of Chemistry). Each volume covers an 18-month period in the literature (July 1979-Dec 1980 and Jan 1981-June 1982, respectively). The coverage of the literature is reasonably comprehensive, although less militantly so than the earlier series. It is also somewhat more critical and evaluative. The volumes are divided into 14 sections, each prepared by one or two individuals who are active in that specialty. The contributors have met the challenge of abstracting the essence of many research investigations, each in a sentence or two. The skill and insight with which this has been done are evident throughout. The series maintains the worthy tradition of tabulating rate constant values and reaction conditions. The coverage, reflecting published activity, is clearly slanted toward transition-metal coordination chemistry, both ligand substitution and redox processes. Organometallic reactions do receive extensive coverage, however, comprising about one-third of the pages in each. Emphasis is on systems in which mechanisms have been examined by quantitative data. These volumes are prices within the reach of individuals and clearly deserve space in the personal libraries of those active in these research areas. Nonspecialists, who would probably have less occasion to access the current literature in this manner, will probably be inclined to rely on library copies. Anything the editor and publisher could do to reduce the 18-month interval between coverage and publication would enhance their utility. James H. Espenson, Iowa State Uniuersity
