,574 Organometallics, Vol. 8, N o . 2, 1989 Book Reviews

Book Reviews

Gmelin Handbook of Inorganic Chemistry. 8th Edition, Ge. Organogermanium Compounds. Part 1. F. Glockling, volume author. U. Kruerke, volume chief editor. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin. 1988. xv + 232 pages. DM 1053.

The Gmelin Handbook is doing a fine job of covering or- ganometallic compounds. In Group 14, the Schumanns have reported on organotin compounds with great diligence and the first volume of the organolead miniseries was published in 1987. Now we have in the present book the first volume of a series devoted to organogermanium compounds.

Over the years, interest in organogermanium compounds has waxed and waned. One of the few research groups that has remained faithful to organogermanium chemistry during the last 30 years is that of Professor Jacques Satgd in Toulouse, and it is fitting that it is Professor Satgd who is coordinator of this Gmelin organogermanium effort. In recent years, activity in organogermanium chemistry has been on the rise again. Re- sponsible for this are new and interesting organogermanium systems: germanium compounds containing multiple bonds be- tween germanium and other elements or Ge=Ge bonds, divalent organogermanium species, hypervalent organogermanium com- pounds, and small-ring compounds containing a germanium atom as a ring member. Also the growing interest of synthetic organic chemists in organosilicon and organotin compounds as reagents for organic synthesis is beginning to be extended to organo- germanium compounds.

The present volume covers organogermanium compounds of type R4Ge, where R = alkyl, cycloalkyl, substituted alkyl, alkenyl, cycloalkenyl, alkynyl, aryl, substituted aryl, and heterocyclic groups, as well as those (CH3)3GeR compounds in which R = alkyl and cycloalkyl. In addition, the opening section of this volume contains a very useful listing of the review literature of organo- germanium chemistry: general organometallic texts which deal in part with organogermanium chemistry, monographs and reviews devoted specifically to organogermanium chemistry, and a large number of reviews and articles on diverse aspects of organo- germanium chemistry.

The coverage of R4Ge and (CH3),GeR compounds is complete through the end of 1985. The literature cited includes journal articles, reviews, monographs, patents, conference reports, and doctoral dissertations.

As an example of the information that is provided about a well-studied compound, we can take tetraphenylgermane. First, the various reactions in which it was formed are given in short paragraphs. Some of these reactions are ones in which Ph,Ge wa: formed only as a byproduct in low yield, but the preparatively useful reactions are clearly identified. Next come sections on the molecule and spectra (PE, NMR, IR and Raman, UV, lumines- cence spectra, bond dissociation energies, and crystal and mo- lecular structure) and physical properties. Five different melting points are given. The only hint the reader is given as to which of these is the correct one is the fact that one of them, 229-231 “C. is cited most frequently. But that, of course, does not guarantee that it is the melting point of pure tetraphenylgermane. The next section brings details of the electron-impact mass spectrum of Ph4Ge, studies of its photolysis and radiolysis, and chemical reactions (with elements, with inorganic compounds, and with organic compounds). A last section deals with catalytic properties of Ph4Ge. Each section has its own group of references, and, in all, 203 refererces dealing with tetraphenylgermane are cited.

Only few organogermanes have been studied as extensively as tetraphenylgermane, and most of the information on the less well-studied ones is provided in tabular form.

The book concludes with an empirical formula index and a ligand formula index. The detailed table of contents also will be useful to the reader.

The Gmelin organogermanium series is off to a good start, and we look forward to further volumes.

Dietmar Seyferth, Massachusetts Insti tute of Technology

Mechanisms of Inorganic and Organometallic Reactions. Vol. 5. Edited by M. V. Twigg. Plenum, New York. 1988. xvii + 466 pages. $85.00.

Volume 5 surveys the literature of mechanistic aspects of in- organic and organometallic reactions from July 1985 through December 1986. This volume, a t 466 pages, is 70 pages shorter than Volume 4. This constitutes the major change in Volume 5.

Electron-transfer reactions (Chapters 1-3) have suffered the most severe cut, from 103 pages in Volume 4 to 67 pages in Volume 5. Chapter 1 on General and Theoretical aspects has steadily declined with 21 pages in Volume 2,18 pages in Volume 3,13 pages in Volume 4, and 3 pages in Volume 5. Chapter 2 on Redox Reaction Between Two Metal Complexes is reduced by about 50% from Volume 4.

The coverage of “Substitution and Related Reactions” in Chapters 4-9 has changed very little from Volume 4. Similarly the coverage of “Organometallic Compounds” in Chapters 10-14 is not appreciably different from Volume 4.

The tabulation of volumes of activation in Chapter 15 remains a very useful component of this book. It would be useful (though perhaps difficult to compile) to have tabulated all activation parameters reported in the 18-month period.

The location of all references in the back of the volume remains a slight inconvenience. The nearly 2-year gap between literature surveyed and publication is perhaps unavoidable but limits the utility of the volume for current literature. “Mechanisms of Inorganic and Organometallic Reactions” is a useful reference for researchers of inorganic and organometallic mechanisms and should be present in reference libraries.

Jim D. Atwood, State University of New York ut Buffalo

New Journal of Chemistry. Special Issue on “Recent Ad- vances in Di- and Polynuclear Chemistry” (Volume 12, Nos. 6-7). P. Braunstein, guest editor. CNRS/Gauthier-Villars, Montrouge, France. 1988. v + 413 pages. FF 490 (about $87). Softcover, All Papers in English.

Various journals have found the publication of special issues devoted to invited papers on a selected topic of some advantage. In this manner, they are able to publish papers by leading authors in a field who normally publish elsewhere, thereby raising, with that issue, the general level of the journal. Also, they obtain the financial benefit of special issue sales to individuals. Such special issues are of greatest value to the individual purchaser when they are composed of authoritative reviews whose usefulness will be reasonably long-lived. A topical collection of research papers will be useful on a short-term basis, but hardly worth purchasing by the individual chemist.

We review here an issue of the New Journal of Chemistry (Nouueau Journal de Chimie) that is devoted to a special topic in an area where inorganic and organometallic chemistry overlap: the synthesis, reactivity, and applications of di- and polynuclear metal compounds. This area has received much attention during the past 25 years, and it has matured a great deal in this time. Twenty-five years ago, the synthesis of cluster complexes was a

Book Reviews

hit-or-miss process, but now synthesis-by-design has become quite common. Also, the reactivity of such complexes has become much better understood, although it is still full of surprises.

The New Journal of Chemistry special issue contains, hig- gledy-piggledy, 6 reviews, 10 communications, and 38 original research full papers. The table of contents does not reveal to the reader to which of these categories a given title belongs. Some of the full papers are identified as “articles”, but most are not. There is no thematic ordering of these 54 papers. All except one of the contributions deal with di- and/or polynuclear complexes that contain transition metals, although in some cases main-group elements are present as well.

Presumably, author participation was by invitation. The re- sulting collection of papers is for the most part a Franco-American effort. An accounting according to the country of the authors gives the following distribution in the number of papers in which these countries are represented: USA, 22; France, 14; West Germany, 6; Italy, 6; Great Britain, 4; Canada, 3; Spain, 2; the Netherlands, 2; Switzerland, Australia, Japan, and Chile, one each. Inspection of the author index shows many of the expected names to be present, but many others are conspicuously absent.

This collection of reviews, communications, and full papers brings some interesting new results, but it does not seem like a worthwhile purchase for the individual reader. A well-chosen collection of reviews covering aspects of di- and polynuclear chemistry would have been much more useful. The six reviews in this issue would have been a good start for such a collection.

The November 1988 issue of Chemical Reviews which brings a collection of 17 reviews devoted entirely to diverse aspects of transition-metal organometallic chemistry stands in marked contrast to this New Journal of Chemistry special issue. Authors from the U.S.A., Canada, Great Britain, West Germany, France, and New Zealand are represented in this excellent and useful collection. At a single issue price of $22, this Chemical Reviews issue is a worthwhile acquisition for the individual organometallic chemist.

Dietmar Seyferth, Massachusetts Institute of Technology

Organometallics, Vol. 8, No. 2, 1989 575

Gmelin Handbook of Inorganic Chemistry. Eighth Edition. Pb. Organolead Compounds. Part 1. Tetramethyllead. F. Huber, volume author. W. Petz, volume editor. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin. 1987. xii + 194 pages. DM 896.

The Gmelin Handbook organometallic compound series to date already covers a major fraction of the metals and metalloids in the periodic table. With the present book a new miniseries on organolead compounds is commencing. For some 50 years, tet- raethyl- and, to a lesser extent, tetramethyllead were, in terms of production and sales, the most important industrial organo- metallic compounds. In recent years, both have been in strong decline as a result of a recognition of the actual and potential environmental hazards associated with their use as antiknocks in the automobile engine. During these years when organoleads were large-scale commerical chemicals, much work was devoted to studies of their synthesis, their properties, and their reactivity. The results of these studies, insofar as they were published or patented, will be covered in the Gmelin organolead volumes. Nowadays, it may be added, research on organolead compounds (excluding environmental studies) is in a significant decline and very few papers on this subject are being published.

The present book deals with a single compound, tetra- methyllead, a compound which because of its commercial im- portance, has been studied in great detail. AU that is known about tetramethyllead is brought here with the usual Gmelin Handbook thoroughness: preparation, spectroscopy, physical properties, chemical reactions, physiological properties and toxicity, uses, and environmental aspects. The relevant literature, which includes journal articles, patents, conference proceedings, monographs and theses, has been covered well nigh exhaustively through 1986, and these references are all cited a t the end of each topical section.

The first 55 pages of this book are devoted to general references: first on organometallic derivatives of the Group 14 elements, then on organolead compounds in general (monographs and reviews;

papers and reviews on physical properties, spectroscopy, analysis, toxicology and use as biocides, uses, and environmental aspects).

This will be a very useful book if you want all the leading references on organolead compounds or if you want to know anything at all about tetramethyllead.

Dietmar Seyferth, Massachusetts Institute of Technology

Organometallic Syntheses. Volume 4. Edited by R. B. King and J. J. Eisch. Elsevier, Amsterdam. 1988. xx + 617 pages. $236.75.

As noted in our review of Volume 3 (Organometallics 1987,6, 684), “Organometallic Syntheses” now publishes syntheses sub- mitted by chemists other than the editors. Those published in Volume 3 were well-chosen and useful ones, and this is the case also in Volume 4. It was the intent of the editors, according to their introduction, “to include procedures that give the safe, reliable syntheses of organometallic compounds that can lay some claim to significance in current chemical research.” With this goal in mind, a book resulted in which are provided detailed procedures for the preparation of some 76 types of transition metal and some 85 main group metal organometallic compounds. This book is an international enterprise, with authors from the USA, Canada, many European countries, and Japan. The authors were well- chosen; usually they are the chemists who developed the proce- dures that they describe or they have used the procedures ex- tensively in their research. Thus, although the procedures have not been checked (as are those in “Inorganic Syntheses” and “Organic Syntheses”), one may be reasonably confident that they will work when one tries them out. Of course, scale-up is another matter: millimole-scale preparations often give trouble when they are carried out on a 0.1-1.0 mole scale.

The readers who use this book would do well to read the Introduction on pages vii and viii. The table of contents is a marvelous cornucopia of organometallic compounds ranging from the exotic to the down-to-earth useful types, but just about all are of current interest.

The book has a two-part index, the first for the metals in the organometallic reagents used and in the products and the second for the ligands or structural features in the organometallic products. The typescripts of the authors were photoreproduced, so the book is not uniform (but not unattractive) in terms of type font and line spacing. Also, it is much longer than a typeset book would have been. The same format that was used in the pres- entation of each synthesis in Volume 3 (equation, introduction, procedure, properties, references) is used here.

The editors may be congratulated: like Volume 3, Volume 4 is an excellent and very useful book. All organometallic chemists will wish to have a personal copy, but it will be an expensive proposition to make that wish come true. In any case, this book, together with the preceding three volumes, should be on the shelves of every chemistry library.

Dietmar Seyferth, Massachusetts Institute of Technology

Organoselenium Chemistry I. Functional Group Trans- formations. By A. Krief and L. Hevesi. Springer, Berlin. 1988. xi + 221 pages. $95.00.

This is the first volume of a two-volume set dealing with or- ganoselenium chemistry. Volume I deals with reactions which do not generally involve isolable selenium-containing interme- diates. Volume I1 will cover selenium-based transformations involving two or more separate steps.

Chapter 1 is a brief, but useful compilation of some of the general properties of selenium: (a) abundance, (b) selenium toxicity in plants and animals; and (c) the physical and chemical properties of elemental selenium. Chapter 2 describes some of the reactions of nucleophilic selenium species. These include inter alia: (a) SN2 cleavage of esters; (b) dealkylations of amines and ammonium species; and (c) deoxygenations of epoxides. Chapter 3,4, and 5 deal with selenium dehydrogenations, selenoxide-based oxidations, and selected reactions of selenenyl halides, respectively. Most readers will probably find these chapters (along with Chapter 11) of limited utility.

576 Organometallics, Vol. 8, No. 2, 1989

Chapters 6 and 7 cover the chemistry of benzeneseleninic anhydride and benzeneseleninyl halides with mildly nucleophilic species, such as phenols, enols, amines, and sulfides. The examples cited in these chapters are well chosen and provide the reader with a good overview of this area. Chapter 8 describes the chemistry of perseleninic acids. These reagents are useful reagents for epoxidations and for Baeyer-Villiger type oxidations. As in the previous two chapters, the coverage of the area is quite good.

Chapter 9, which deals with the chemistry of selenium dioxide, is by far the largest and most exhaustive chapter in the book. Since the last major review of this area was published over 10 years ago, this chapter will be important reading for anyone involved with selenium dioxide reactions of all sorts. This chapter, together with Chapter 10 which deals with imidoselenium compounds, thoroughly covers the regio- and stereoselectivity of reactions of selenium dioxide and related species. As a result of the extensive compilations of reactions, the reader is provided with an excellent review of this area.

In general, the material described in Volume I is clearly presented. In fact, the only real problem with Volume I is that it is difficult to assess its value without also examining Volume I1 (which, of course, is not yet available). If the presentation in Volume I1 is equally thorough, then the two-volume set will be a useful addition to most libraries.

Dennis Liotta, Emory University

Book Reviews

Gmelin Handbook of Inorganic Chemistry. Eighth Edition. Sn-Organotin Compounds. Part 14. Dimethyltin-, Di- ethyltin- and Dipropyltin-Oxygen Compounds. 1987. xiv + 248 pages. DM 1119. Part 15. Dibutyltin-Oxygen Compounds. 1988. xiv + 442 pages. DM 1918. Herbert and Ingeborg Schumann, volume authors. U. Kruerke, volume editor. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin.

There are many references in “Chemical Abstracts” that mention dialkyltin-oxygen compounds, especially patents, because this general class of organotin compounds has found many ap- plications: as stabilizers for poly(viny1 chloride) and other organic polymers, as biocides of various kinds, and as catalysts for con- densation reactions, as well as others. Of the dialkyltin-oxygen compounds, the dibutyltin derivatives have been the most im- portant, and it required a separate book of over 400 pages to do these justice. Part 14, the book describing dimethyl-, diethyl-, and dipropyltin-oxygen compounds, is much shorter.

Part 14 begins with some general references: first some dealing with the organometallic compounds of the main group IV elements and with organotin compounds (reviews, papers on physical and spectroscopic properties, analysis, toxicology and biocidal use, general uses). These represent an updating of such general references as collected in earlier volumes of this series. Under “Uses”, the list of patents is about 12 pages long. The patent titles are given, but for most of these it is not a t all clear what organotin compounds are involved and what role they are playing. What, for instance, is the reader to make of a patent listed here entitled “Antidandruff Hair Care Compositions”?

After the general references, there is a short section of general references on organotin-oxygen compounds: preparation and reactions, physical properties, toxicology, and uses. Then the coverage of the individual compounds begins with the hydrated dimethyltin ion, [ (CH3)2Sn(Hz0),]2+, and continues with (CH3)2Sn(OR)2-type compounds of all kinds, dimethyltin di- carboxylates, (CH3)2Sn(02CR)2, and dimethyltin derivatives of inorganic oxyanions and more specialized dimethyltin-oxygen compounds. The same type of coverage is repeated for diethyl- and dipropyltin-oxygen compounds and then, in Part 15, for dibutyltin-oxygen compounds. Part 15, however, as mentioned above, is much larger than part 14, not just because much more work has been devoted to dibutyltin-oxygen compounds but also because under “Uses” of the commercially important compounds there are extensive patent listings. For the commercially sig- nificant di-n-butyltin dilaurate the patent list requires 101 pages and for di-n-butyltin maleate, 15 pages. Again, only the patent titles are given, and, by themselves, they have little, if any, in- formation value as far as these dibutyltin dicarboxylates are concerned. There is a point beyond which exhaustive literature coverage no longer makes sense, especially a t such a high per page cost.

The individual compound descriptions are thorough as always. For di-n-butyltin diacetate, for instance, there is provided fully referenced, detailed information on its preparation, physical and spectroscopic properties and reactions, and its toxicity and biocidal activity and uses. For less well-studied compounds the available information usually is provided in tabular form.

Both books have a detailed, useful table of contents and con- clude with empirical formula and ligand formula indexes.

Diorganotin oxides, which may be of interest to some readers, are oligomeric or polymeric and, as polynuclear species, will be covered in a later volume of the Gmelin Handbook organotin compound series.

Dietmar Seyferth, Massachusetts Institute of Technology