606 Organometallics, Vol. 5, No. 3, 1986
Rook Reviews
Book Reviews Metallo-organic Chemistry. By A. J. Pearson. Wiley, New York. 1985. xi + 398 pages. $29.95. As the title suggests, this book is aimed primarily at the organic chemist who desires a preliminary education in the burgeoning area of organometallic chemistry. The objective is to provide coverage of the basic aspects of organometallic chemistry in the context of reactivity patterns and to rationalize these trends in terms of simple frontier molecular orbital theory. The author is a researcher who has demonstrated the application of many organometallic compounds to organic synthesis, and the text is liberally sprinkled with examples of useful stoichiometric and catalytic reactions promoted by transition-metal complexes. The first chapter on the basics of bonding and electron counting involving metals and a variety of organic ligands (20 pages) may seem rather cursory to the inorganic chemist but actually does a good job of providing the minimum necessary introduction to these vital concepts. Chapter 2 surveys common properties and reactions of organometallic compounds, including fluxional behavior, oxidative addition and reductive elimination, a- and pelimination, and insertion reactions. Also included are discussions of important catalytic reactions, such as olefin metathesis, hydroformylation, polymerization and oligomerization, Wacker oxidation, epoxidation, and hydrogenation. Important principles are emphasized, with concentration on mechanisms and the significance of these reactions in the synthesis of organic molecules. The use of transition-metal centers for the stabilization of reactive organic species is also covered in this chapter. After covering basic principles, and also after convincing the reader that organometallic chemistry is of some use to an organic chemist from a number of viewpoints, the author uses the remaining seven chapters to discuss in more detail the synthesis, properties, and chemistry of metal-carbon bonded compounds. The arrangement of material here is sensibly organized by the hapticity of the organic ligand, beginning with alkyl compounds and leading on to polyhapto ligands. Each chapter contains appropriate literature citations, many of them review articles, and salient references through mid-1982 are included. The book is remarkably free of typographical errors, and the structural drawings are well presented. This publication is one of a number of recent offerings in this area and in my opinion will be a useful text for those organic chemists whose background in this important area is deficient and who desire a basic introductory text. However, no problems are provided after each chapter, a deficiency if the book is to be used as a teaching text. The price is reasonable and places this book within the reach of any student. Russell P. Hughes, Dartmouth College
Gmelin Handbook of Inorganic Chemistry. 8th Edition. Thorium. Supplement Volume E. Coordination Compounds. K. W. Bagnall and B. Kanellakopulos, volume authors. C. Keller and K.-C. Buschbeck, volume editors. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenchaften and Springer-Verlag, Berlin/Heidelberg/New York. 1985. xviii + 322 pages. DM 988, $368.66. The present volume represents part of the Gmelin Institute’s recent effort to update the treatment of radium and the actinide elements in its “Handbuch der Anorganischen Chemie” series. Supplement Volume E of the 8th edition is authored by Professors Kenneth W. Bagnall of the University of Manchester and Basil Kanellakopulos of the Kernforschungszentrum, Karlsruhe. Although this volume is entitled, “Coordination Compounds”, the terminology is employed in the broadest sense, and there is an extensive treatment of thorium organometallic compounds. Coverage of the literature extends through the end of 1983.
The organization of this monograph is by ligand type. Section 1deals with “Complex Compounds of Thorium” and is subdivided into an introduction, complexes with neutral donor ligands (e.g., amines, phosphorus donors, oxygen doors), 1,3-diketones (e.g., acetylacetonates), tropolone and related ligands, 8-quinolinol and related ligands, cupferron and related ligands, dialkylcarbamates, Schiff bases, other ligands (e.g., poly( 1-pyrazolyl)borates),and phthalocyanines. The second section deals with organometallic compounds of thorium and treats in successive subsections, allyl compounds, cyclopentadienyl compounds, compounds with substituted cyclopentadienyl ligands, indenyl compounds, compounds with alkylated indenyl ligands, cyclooctatetraene compounds, compounds with substituted cyclooctatetraene ligands, and benzocyclmtatetraene compounds. In both sections, the coverage is well-organized and in-depth. The wealth of information provided for each compound includes synthetic approaches, spectroscopic data, color, melting point, crystal structure information, and reaction chemistry. There is an abundance of well-produced figures illustrating molecular structures and other physical data. As in all Gmelin volumes, the present monograph provides a detailed index (in this case by ligand formula) as well as a key to the Gmelin classification system and a table of conversion factors. The price of this volume is obviously prohibitive for most individual researchers; however, it should not deter libraries from investing in such a valuable reference book. All researchers interested in actinide coordination and organometallic chemistry will find this successful volume to be a useful addition to the Gmelin series. Tobin J. Marks, Northwestern University
Fundamental and Technological Aspects of Organo-f-Element Chemistry. Edited by T. J. Marks and I. L. Fragali. D. Reidel Publishing Co., Boston-London-Dordrecht. 1985. xiv + 414 pp. $56.00. This book contains 11 of the main papers presented at the September 1984 NATO Advanced Study Institute on organo-felement chemistry. Like the earlier volume, “Organometallics of the f Elements” (edited by T. J. Marks and R. D. Fischer), on the first NATO AS1 on organolanthanide and organoactinide chemistry, this book constitutes a major resource in the area. The editors (who also organized these conferences) are to be commended for putting in the extra effort needed to make the conference proceedings generally available to the chemical community through these books. This volume includes chapters on organometallic chemistry by Schumann, Kagan, Streitwieser, Takats, Teuben, Marks, and Day. Many of these papers contain valuable information not published in any other form. Also included are an excellent introduction to f-element optical spectroscopy by Edelstein, a critical discussion of f-element NMR spectroscopy by Fischer, and comprehensive surveys of f-element photoelectron spectroscopy, photochemistry, and catalysis. This collection of lectures by some of the best f-element chemists in the world is an excellent source of recent results in this area. William J. Evans, University of California, Irvine
Carbocation Chemistry. By P. Vogel. Institut de Chimie Organique, Universite de Lausanne, Switzerland, and Elsevier, Amsterdam. 1985. xiv + 596 pp. $129.75. Pierre Vogel succeeded in writing a very readable book presenting many basic concepts of modern chemistry through the study of carbocations. Emphasis is given to structure-stability and structure-reactivity relationships. Structural aspects of carbocations in solution and as solids is compared with a thoughtful discussion of substituent effects and solvation. Gaseous ions and their thermochemistry are also discussed and related to solution chemistry. This is followed by chapters on carbocations as reactive intermediates and rearrangements of the ions. Par-
Book Reviews ticularly interesting is the discussion of carbocations and organometallic complexes, bringing together interesting aspects of transition-metal complexes and their carbocation analogues. The concluding chapter discusses carbocations in synthesis, rounding out the number of significant topics condensed in a book of 600 pages. Obviously such a broad scope coverage cannot be all encompassing, and the author made his own choices of preference. This is, however, not detracting from the value of his book. The book reflects Vogel’s individual taste which is even demonstrated by such intriguing subheadings of the introductory chapter as “Stable Carbocations and Red Wine” followed by “The Aging of Red Wine and Transient Carbocations” leading to the more trivial “Gibbs Energy Diagrams”. I frequently wondered how to catch my students’ early interest for carbocations and to condense a very large and complex field into manageable proportion. I must say to have learned much on all counts from Vogel’s book. The only negative note on this highly recommended book, well suited for advanced students and researchers alike, is its prohibitive price. It will regretfully limit its availability to libraries and even so to only the better endowed ones. George A. Olah, University of Southern California
Dictionary of Organometallic Compounds. J. Buckingham, executive editor. Chapman and Hall, London, New York, and Toronto. 1984. 3232 pages (in three volumes). $990. As stated in the preface, “the aim of this publication is to review the whole field of organometallic chemistry, to select those compounds which are in the opinion of the specialist Editors most typical, representative, interesting, and useful or potentially useful, and to present their properties and selected bibliography in an orderly and systematically indexed fashion.” The work is organized into three volumes, two of which contain compounds of all elements except the halogens, noble gases, unstable radioactive elements, H, C, N, 0, P, S, Se, and Te listed alphabetically according to the element; Volume 1contains Ag-Mn and Volume 2, Mo-Zr. At the beginning of the section on each element is up to one page of useful information for quick reference concerning physical properties, availability, handling, toxicity, isotope abundance, spectroscopy, analysis, types of compounds covered, and references to books and reviews. Approximately 15000 entries are found in these two volumes, all the way from one for Bk to 2222 for Fe. They are listed according to the molecular formula starting with C and H and proceeding with other elements in alphabetical order. Counterions of cationic or anionic entries are not part of the molecular formula. At the beginning of each section is a compilation of structural formulas for each entry, as far as the structures are known. The compilation is extremely useful for quick, visual searching. Each compound is listed by empirical formula, one or more names, and a CAS registry number. The compound’s physical properties are then described to the extent that they are known, and any hazards or toxicity noted. The compound’s use or importance (first of its kind etc.) is sometimes noted, although this practice is dependent upon the knowledge and dedication of the author for the section on that element. Each entry concludes with references and points out what can be found in each (preparation, X-ray structure, IR, NMR, etc.). One negative feature is that the referencing is sometimes sloppy. For example, the first report is sometimes omitted in favor of a later, usually more complete, report by a different author; both should be included. Et al. is also misused; papers by two authors, A and B, are listed as being written by “A, et al.”, and in a t least one case, even more annoyingly, the same paper is referenced several times as being “B, et al.”. Surprisingly, however, I found few names misspelled or wrong initials used. The third volume contains a name index, a molecular formula index, and a CAS registry number index. The name index is of limited use since many compounds can be named in several ways. For example, a “trineopentyl” zirconium complex is listed, but Ta(CH-t-Bu)(CH,-t-Bu)3 is listed only as “tris(neopenty1)neopentylidene/tantalum”. There is the occasional gaffe; for example, [W(C-t-Bu)Cl,]- is listed as “tetrachloro(1,l-dimethylpropylidyne)tungsten(l-)”, instead of 2,2-dimethylpropylidyne. I found the molecular formula index to be more useful. One way in which the dictionary could be improved is to note which compounds have analogues containing another metal. For
Organometallics, Vol. 5, No. 3, 1986 607 example, Mo(CO)&CPh2)is known for M = Cr, Mo, and W. Each compound is listed in the appropriate section (apparently care was taken to list all compounds in this case and in several other cases that I spot-checked) but each listing did not note that analogues containing two other metals are known. The additional space required to do so would be minimal. One of the main weaknesses of the dictionary is inherent in a work of this type, and that is that selections are a t times somewhat subjective and/or random. One of the main strengths is that one can get an idea quickly as to how much work has been done on a given element and what are some of the major types of compounds available. Since references to other sources are included, the dictionary can be a good place to start. The dictionary will be most useful to those who have little knowledge of other sources, or those, knowledgeable or not, who are well-heeled enough to afford to have their own copy a t their fingertips. It certainly should be a required reference for any library. Richard R. Schrock Massachusetts Institute of Technology
New Frontiers in Organometallic and Inorganic Chemistry. Edited by Y. Huang, A. Yamamoto, and B.-K. Teo. Science Press, Beijing. Published in the USA by S.P. Richards Publ., New Providence, NJ. 1984. xxix + 527 pages. $59.50. This book brings the 39 plenary lectures and the 49 posters presented at the Second China-Japan-USA Trilateral Seminar on Organometallic and Inorganic Chemistry in Shanghai in June 1982. Most of the Japanese and American work reported here will have been published in the meantime (if it had not been published already before the meeting took place), so it is the Chinese work which will be of main interest to the reader. Reports of Chinese research in areas of current interest and fashion show that they are working hard to catch up after their difficult years. Lectures or posters on, for instance, cluster chemistry, organolanthanide compounds, transition-metal-catalyzed polymerization, metalloporphyrins, iron-sulfur complexes, arsenic ylides, organic compounds of early transition metals, and organosilicon chemistry are found among the Chinese contributions in the book. The names of the Chinese authors for the most part will not be familiar to most readers of this journal, but no doubt this will change in the future since research activity in chemistry in the People’s Republic of China is increasing steadily. This is not a book that individuals will want to purchase, but it is one that chemical libraries might want to have. Dietmar Seyferth, Massachusetts Institute of Technology
Organosilicon and Bioorganosilicon Chemistry: Structure, Bonding, Reactivity and Synthetic Application. Edited by H. Sakurai. Ellis Horwood Ltd, Chichester, and Halsted Press (Wiley), New York. 1985. 298 pp. $46.95. The present book brings the 27 Plenary and Invited Section Lectures presented at the Seventh International Symposium on Organosilicon Chemistry which was held in Kyoto in September 1984. The title of the book is misleading: only one of the 27 papers (that by R. Tacke) deals with bioorganosilicon chemistry. The subject matter of the other 26 papers is heavily slanted toward the currently popular research areas of organosilicon chemistry: compounds with multiple bonds involving silicon, reactive silicon-containing intermediates, and organosilicon compounds in organic synthesis. Among the authors are the expected names, well-known to those who follow organosilicon chemistry: West, Brook, Wiberg, Bock, Davidson, Gaspar, Weber, Watanabe and Nagai, Gusel’nikov, Eaborn, Corriu, DunoguBs, Liu, Fleming, Tamao, and Lukevics. Several interesting papers that do not involve the abovementioned areas of currently fashionable and popular organosilicon research are worth noting: mechanistic studies of the new group-transfer polymerization procedure, which involves silyl ketene acetals as reagents, by Sogah and Farnham of Du Pont; the synthesis of sila drugs and microbial transformations of organosilicon compounds, by R. Tacke; the conversion of some polyorganosilicon precursors to ceramics, by R. H. Baney and co-workers at Dow Corning. Also of interest to your reviewer was Tadashi Wada’s account of past and current trends in the silicon
