Organometallics, Vol. 2, No. 1, 1983 201
Book Reviews
Book Reviews Gmelin Handbook of Inorganic Chemistry. 8th Edition. Fe. Organoiron Compounds. Part A. Ferrocene 5 (in German). J. Fussel, volume author, A. Slawisch, volume editor. 1981. iv + 379 pages. DM 998. $464.60. Organoiron Compounds. Part B. Mononuclear Compounds 7 (in English). A. Slawisch, volume author and editor. 1981. i + 258 pages. DM 718. $331.90. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin/Heidelberg/New York. Ferrocene was reported first in 1951 and shortly thereafter Woodward and his co-workers carried out the first studies of the organic chemistry of this novel aromatic compound. In the intervening 30 years the development of ferrocene chemistry has become a worldwide endeavor. The Gmelin Institute’s ambitious plan to include all ferrocene derivatives in its organoiron coverage has given us six volumes to date (Ferrocen 1-4, 6, and 7). This is part 5 of the ferrocene series which covers mononuclear, monosubstituted ferrocenes whose substituents contain elements other than C, H, halogen, 0, or N. Included in this volume are such ferrocenes whose single substituents contain elements of group 6 (S,Se), 5 (P, As, Sb), 4 (Si, Ge, Sn, Pb), and 3 (B, Al, Tl), transition elements (Ti, Zr, V, Cr, Mo, W. Mn, Co, Ni, Fe and the platinum group metals), coinage metals (Cu, Ag, Au), and uranium. Thus this volume is doubly organometallic. The ferrocenyl substituent, within the limits set by its oxidative instability, can play the part of phenyl, and it has been a great sport to transfer as much benzene chemistry as possible to the ferrocene system. This has produced many new compounds. Add to the compounds generated by this approach those ferrocenes in which the Cl,,”ge group is simply going along for the ride while functional group transformations are being effected in more remote parts of the molecule, and the number of ferrocene derivatives in existence becomes legion. But the Gmelin net (courtesy of “Chemical Abstracts”) catches them all and presents them to the reader nicely organized and ordered, as has been done in this volume devoted to the organometallic derivatives of ferrocene. Preparation, physical and spectroscopic properties, electrochemistry, chemical reactivity, and applications all are covered. Of these many compounds no one compound has received the detailed study that ferrocene itself has received, so much of the data are presented in tabular form. The book closes with a formula index for Ferrocene volumes 1 through 5 . The seventh volume of the mononuclear iron compound series also closes with a formula index-for parts B6 and B7. The iron compounds which it treats include (q4-cyc1obutadiene)iron tricarbonyl and its ring-substituted derivatives and complexes which contain a t least four carbon atoms in a 5-membered cyclic diene system which is a bonded to an iron atom. The fifth atom may be a heteroatom (B, group 4, group 5, S), so in this category fall the Fe(C0)3 complexes of, for instance, the silacyclopentadienes and phosphacyclopentadienes. However, in most examples the fifth atom is carbon, giving (~~~-cyclopentadiene)iron tricarbonyl and its derivatives. Of the compounds covered in this volume, only the much-studied q4-C4H,Fe(C0)3rates multipage treatment, and the bulk of the book deals with this compound and its many derivatives. In this book also the usual thorough Gmelin treatment of all aspects of all the published work on the compounds covered is encountered. The literature closing date for this book is the end of 1980, for the ferrocene volume it is mid-1981, so the reader interested in one of these areas will have to search only the more recent literature if he wants to be up-to-date. However, tempus fugit and organoiron chemistry is a very popular field of research, so these books and their companion volumes will soon need to be brought up-to-date with supplements.
The ferrocene volume is an “old” Gmelin: it is written in German, but Part B7 is written in English. Both are worthy additions to the ever-growing organoiron series. Dietmar Seyferth, Massachusetts Institute of Technology
Mossbauer Spectroscopy and Its Chemical Applications. Advances in Chemistry Series No. 194. Edited by J. G. Stevens and G. K. Shenoy. American Chemical Society, Washington, D.C. 1981. xiii + 642 pages. $69.95. This book brings together selected lectures from a symposium jointly sponsored by the divisions of Nuclear Chemistry and Technology and Inorganic Chemistry a t the ACS meeting in Houston, March 1980. Specifically, the book is composed of seven long invited papers and more than 20 short papers. Six of the long papers contain reviews of some of the areas in which Mossbauer spectroscopy is making a substantial contribution a t the present time: chemical bonding, environmental applications, analytical applications, biological applications, phase analysis, and energy and catalyst applications. The other review documents the recent development of conversion electron spectroscopy and its application mainly to surface science. The short papers generally relate to the above six topics. However, there are very useful chapters on recent advances in the use of Mossbauer isotopes (lS7Au,67Zn,237Np,lZ1Sb,lZ7I,lmI, lZ6Te,and w R ~other ) than the widely used 57Feand ‘19Sn which are the focus of the other chapters. Of the 29 chapters, about 1 2 will be of interest to the inorganic and organometallic chemist. The chapter by T. K. Sham et al. provides a very good review of the lg7Auliterature. From their theoretical interpretation, the u-bonding properties of a host of ligands bonded to Au are obtained. The chapter by E. Munck provides a timely overview of the contribution that Mossbauer spectroscopy and EPR have made to the structure of the ironsulfur clusters which have emerged recently from biological systems. 237NpMossbauer studies have been especially valuable in the study of bonding in N p compounds, as is outlined by Karraker in the chapter on Np(1V) organometallics. The scope of the chapters by Parish and Birchall on lZ1Sband lnI Mossbauer is somewhat narrower than the above three chapters. They describe studies of compounds from reaction of ketimines with SbC1, and polyhadide cations and anions of I, respectively. The longest chapter in the book by Gutlich describes fascinating and detailed studies of spin crossover in iron compounds while the short chapter by Long et al. provides a fine example of the study of spin state transformation at high pressure in an iron pyrazollylborate compound. Several chapters toward the end of the book provide useful overviews of the use of Mossbauer spectroscopy in metallization of plastics (Cohen), mixed-metal (Fe, Ru) catalysts (Good et al.), zeolite-iron catalysts (So et al.), oxidation catalysts (Berry), and supported catalysts (Ying-ru). This book emphasizes the interdisciplinary uses of the Mossbauer effect in most scientific disciplines. The book is well produced, and the papers are of very high standard for this kind of a conference proceedings. For any practicing Mossbauer spectroscopist, this book is important to have on the shelf. The organometallic or inorganic chemist working in the area of the chapters described above should make sure that his library has a copy. G. M. Bancroft, University of Western Ontario
Organic and Bio-organic Chemistry of Carbon Dioxide. Edited by S.Inoue and N. Yamazaki. Kodansha Ltd., Hallsted Press. Wiley, New York. 1982. xi + 280 pages. $49.95. The chemistry of carbon dioxide is reviewed in this book in six chapters by different authors. Throughout this book, many
202 Organometallics, Vol. 2, No. 1, 1983 of the references are to Japanese language publications. This reflects the volume of Japanese research in this field but unfortunately highlights these works’ inaccessibility, except through such reviews, to the almost totally monolingual English world. It is also regrettable that this 1982 book, with very few exceptions, taps the literature only through 1978. The authors of this book have produced a readable, well-written work with very few language problems or “typos”. The various chapters are good reviews of the respective areas for scientists new to the field. There is a useful, detailed Table of Contents and a small index. A much expanded index would greatly facilitate retrieval of information from otherwise not cross-referenced chapters dealing with the same subjects. A chapter on organic syntheses with carbon dioxide by E. Haruki reviews, in detail, “recent” organic chemistry with C 0 2 . This chapter provides good detailed discussions with copious references. Haruki discusses the Friedel-Crafts reaction of aromatics carboxylation with C 0 2 in the presence of AlCl, but does not mention the increasing volume of research on the COZ/H2 methanol Fischer-Tropsch type reactions. This chapter includes sections on the Kolbe-Schmitt reaction and reaction of C 0 2 with amines, among various other reaction types. The next chapter by T. Ito and A. Yamamoto on “Organometallic Reactions of Carbon Dioxide” summarizes the literature in this area-through approximately 1978. There are a number of good, more recent research reports that unfortunately were not included. The first table and associated text in this chapter purport to present many thermodynamically favorable reactions utilizing C02,but only favorable enthalpy changes are shown and the harmful entropy changes are not mentioned. Consideration of AG’, not just AH,shrinks the list of favorable reactions drastically. Thus, the proposed direct carboxylation of aromatic or olefinic hydrocarbons discussed later is not viable. This chapter does summarize well the wealth of non-transition metal, transition metal, and catalytic reactions involving C02 The chapter would be well served by discussing, a t least briefly, not just organometallic chemistry starting with carbon dioxide but also the extensive CO C 0 2 work such as J. Lewis et al’s Os cluster bound C 0 2 and the numerous water-gas shift studies. As discussed in this chapter, readers should beware that most claimed COz “adducts” are poorly characterized and may be other types of complexes. This chapter states that a necessary step in the catalytic utilization of C 0 2 is its preliminary insertion into a M-A (A = H, C, N, or 0)bond. Not so. The authors do subsequently cite work by M. H. Chisholm et. al. which demonstrates another pathway. Chapter 4 by S. Yamazaki, F. Higashi, and S.Inoue is on “Syntheses of Macromolecules from Carbon Dioxide”. Condensation, ring-opening, and addition polymerizations are reviewed. This is followed by a chapter by K. Asada on “Biological Carboxylations” which reviews photosynthetic carboxylations. The last chapter on “Model Reactions of Biochemical Carbon Dioxide Fixations” by S. Inoue includes discussion of carbonic anhydrase, biotin, and related systems and urea formation. These chapters treat, in an introductory fashion, these research areas. T. Herskovitz, E. I. d u Pont de Nemours and Company
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Book Reviews contains two chapters: a long one (344 pages) on “Allylic and Benzylic Carbanions Substituted by Heteroatoms”, by J.-F. Biellmann and J.-B. Ducep, and a short one (46 pages) on “Palladium-Catalyzed Vinylation of Organic Halides”, by R. F. Heck. The first chapter deals with active metal reagents whose allylic or benzylic groups contain C-halogen, C-0, C-N, C-S, C-Se, C-Te, C-P, C-Si, or C-B bonds and encompasses a broad range of functional groups. The discussion covers the basicity of these reagents, their structures in solution, their preparation (principally by metalation reactions), modes of decomposition, their reactions with electrophiles, the regioselectivity and the stereochemistry of their reactions, transformations of derived products, and applications in synthesis. The most vexing problem in their use is regioselectivity control since so many fadom are important: nature of the heteroatom-containing group, other substituents on the allylic system, the nature of the conjugated system, the counterion, the solvent, the electrophile, and the reaction temperature. Although there is still much to be learned on this subject, it is very useful to have what is known summarized in this manner. Six detailed experimental procedures gleaned from the literature follow the discussion, and these seem to have been chosen to illustrate the use of different metalating agents. A 268-page tabular survey of examples of the applications of heteroatomsubstituted allylic and benzylic metal reagents follows. A total of 630 references are cited in this chapter, with a literature cutoff of December 1979. The authors may be congratulated on accomplishing what must have been a tedious task of winkling out all of these examples. While some are easily found in papers devoted to this specific topic, probably many more are hidden away in synthetic papers in which such reactions are used but do not receive special emphasis. The second chapter cites 75 references and is devoted to a much more restricted topic: the Pd-catalyzed vinylation of organic (mostly aryl, vinyl, and benzyl) halides.
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Organic Reactions. Volume 27. W. G. Dauben, editor-in-chief. Wiley, New York. 1982. vii 405 pages. $45.00.
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Volume 27 of this well-established and well-received series
This is a reaction which the author pioneered. The discussion of mechanism is followed by a survey of scope and limitations, eight selected experimental procedures from the literature, and a 24-page tabular survey of the applications of this reaction in the synthesis of substituted olefins. Within its limitations, this is a useful reaction which accomplishes its task in one step, often in good yield. This volume of “Organic Reactions” should be of interest to many readers of this journal since both chapters deal with organometallic topics. The authors have done their job well and have provided two useful additions to the organometallic review literature. Three indexes are provided: a subject index for the present volume, a chapter and topic index, and an author index for all 27 “Organic Reactions” volumes. The price of this book is reasonable, compared with the high prices of many other monographs which are being published these days. Dietmar Seyferth, Massachusetts Institute of Technology
