book reviews Elements of Organometalllc Chemlstry
F. R. Hartley, University of Southampton. The Chemical Society, Burlington House, London, 1974. vi 103 pp. Figs. and tables. 14 X 21.5 cm.
+
I t is hardly a secret that organametallic chemistry has heen thriving and growing st an impressive pace, particularly since 1951 when Kealy and Pauson prepared ferrocene by accident thereby opening possihilities for a whole new range of transition metal compounds. The increasing importance of this field to the discipline of ehemistry is being felt in the appearance of organometallic chemistry even in the undergraduate curriculum (although there is not yet universal agreement about a t what level the aooearance oueht to aecurL Whether one wt-hes tt, ~ntruducethe w h ~ e c tas p a n of the advanced wganlr course, the senror inorganic course, or a t the first year graduate level, Professor Hartley's useful manograph (intended as an introduction to the subject of organometallic chemistry for teachers in the British equivalent of high schools) will be worth consideration. The hook consists of seven chapters: a n Introduction, Preparation of Organometallic Compounds, Structures of Organomet a l k Compounds, Bonding in Organametallic Compounds, Systematic Chemistry of Organometallic Compounds, Homogeneous and Heterogeneous Catalysis, and School Exoeriments in Oreanometallic Chemistnr he rhrmlitry of &I rarhonyls and rya. mdes i r excluded: the treatment focuses on other compounds emtainlng metal-carbon bonds: carbenes, alkyls, aryls, acyls, and T-complexes. Although compounds of the representative elements are not ignored, the emphasis is on those of the transition metals.
..
I t would obviously be impossible to do complete justice to so vast a field in a brief monograph. The author has, however, selected topics wisely and written with a sufficient clarity to make this little hook an excellent basis on which students can build a more complete and sophisticated picture. Hartley treats a number of questions that would orwr naturally to a beginner in the field hut that are seldom drveloped soecificallv in othcr books. Tu wit Chaoter i d e a l s with the question of why organoket a l k compounds which often have AGO > 0 can be prepared a t all. The very brief Chapter 6 outlines the advantages and disadvantages of homogeneous and heterogeneous catalysis in the preparation of organic compounds via organometallie interrnediates. Ligands m e classified according to the number of carbons bonded to the metal rather than by number of electrons donated Along wrth some plau-lhlr (hut arbitrary) simple rules, thm p t r m m the novice t o hookkeep electrons and compute oxidation states for metals in these complexes without facing the difficult question of their precise electronic structures. The chapter on bonding dwells on metalmethyl and metal-ethylene bonds as the paradigms of o-donation and of s-donation with T hack-donation, respectively. A convenient chart provides pictorial representations of filled and empty ligand orbitals for d i g a n d s up through benzene so that the reader can work out the possible overlaps with metal orbitals of appropriate symmetry. That this chapter seems less satisfying results from the difficulty of discussing the electronic structures of organometallics w i t h o d t h e explicit use of group theory or molecular orhital energy diagrams. The level of sophistication that such a treatment of bonding demands is, of course, beyond the bounds set by the author for the
hook as a whole. Nevertheless, I fear that beginning students may remain somewhat mystified after reading this particular chapter. In size and level this book invites comparison with the now ten-year-old Rochow text "Organometallic Chemistry." I t does not contain the large number of practical applications that Roehow features. Hartley's hook dwells to a considerable (perhaps even excessive) extent on transition metal chemistry while Roehow's almost ignores transition in favor of representative metals. The increased emphasis 06 and sophistication of bonding considerations by Hartley reflect the advances of the last decade. Thus, these two monographs are in a certain sense complementary although Hartley's ia of course the more current. The price is reasonable and the text practically error free (although there is an extra H in one of the structures in reaction 108). This book could well precede the more advanced approach in Cotton and Wilkinson or Coates. John J. Alexander University of Cincinnati Cincinnati. Ohio 45221 Fluorine In Organlc Chemistry Richard D. Chambers, University of Durham, England. John Wiley & Sons, New York, 1974. xv 391 pp. Figs. and tables. 15.5 X 23.5 cm. $19.50.
+
The publication of this authoritative work by one of the leaders in the field will be welcomed by all idvestigators in this research area and those who wish to become acquainted with the scope and potential of this rapidly eapandina field. Since the book provides a h r o a d perspective of the role of fluorine in oreanic cbemistrv. ,. it will be of general interest, uhilc serving the needs of spcc~al~sts. Vmsuver, the hook a e,pcrially valuable as a lext in nn advanced special topics course. The author has fulfilled admirably his objective of presenting an outline of organic fluorine chemistry on a broadly mecha(Continued on page A274)
Volume 53, Number 5. May 1976 / A271
book reviews nistic basis. The text consists of ten chapters including, in sequence, a hrief general discussion of the field; preparation of highly fluorinated compounds; selective fluorinations; influence of fluoraearbon groups a n reactive centers; nucleophilic displacement of halogen from fluorocarbon systems; elimination reactions; polyfluoroalkanes, alkenes, and alkynes; functional compounds containing oxygen, sulfur, and nitrogen; a long chapter (73 pages) on polyfluoroaromatie eompounds (in which the author has made major contributions); and organometallic compounds. The chapter on t h e influence of fluorocarbon groups on reactive centers provides a good treatment of the electronic effects of perfluoroalkyl groups on acidities of acids and alcohols and an excellent discussion of fluorocarbocations and fluorocarbanions. I was a bit disappointed that no mention was made of the significant effects of high fluorination on the properties (e.g., infrared spectra, keto-end equilibria) of ketones, P-dicarhonyl compounds, and a.0-unsaturated carbonyl systems, perhaps reflecting the reviewer's bias. The entire presentation is lucid and well organized and the bibliographic material (through early 1972) is quite thorough. Mechanisms are liberally interspersed in the discussion. I noted few errors, e.g., reference 54a (p. 96) is missing and the formula on the bottom of page 102 should he ShF4-F rather than SbF3-F. In contrast to other works in the field, uir., Sheppard and Sharts, "Organic Fluorine Chemistry" and Hudlicky, "Chemistry of Organic Fluorine Compounds," detailed tabulations are absent. Instead, the author has given us a highly readable and enjoyable book on organic reactions involving fluorine, which should be on the shelf of anyone interested in this subject. Robert Filler lllinois lnstlMe of Technoicgy Chicago, Illinols 60616
Organlc Syntheses Vla Boranes
Herbert C. Brown, Purdue University. John Wiley and Sons, New York, 1975. xix 283 pp. Figs. and tables. 23.5 X 15 cm. $17.50.
+
The author's hope "that this book will serve to acquaint working chemists, teachers, and students with the chemistry and techniques of arganoborane chemistry," is a very modest expectation indeed. The book will do this function excellently and will s t the same time provide valuable information in areas that hooks rarely cover. It is in a sense three concurrent books and each will provide the careful reader with its own message. ~ 2 7 4/ Journal of Chemical Education
I t is first a simply written hut highly knowledgable source of information on the ehemistrv and teehniaues of omanohorme chemist&. The additibn of the-chapter a n laboratory operations with air sensitive substances provides information unavailable elsewhere on simple hench-top methods. The potential utility of this book t o organic chemists on the level of "What Can he Done?," and "How to do it?" is douhtlessly high. The second concurrent book is read as a tapestry of 19 years of extremely successful research. What emerges are insights into the planning and development of a research program. This is typically not the mast developed strength of most chemists and sadly it is never taught. Given that one finds an interesting reaction such as the facile addition of horon-hydrogen bonds to carbon-carbon multiple bonds, what then? How do you marshall your forces so that some years later the fabric of organic chemistry is changed and every elementary organic chemistry texthwk includes hydrohoration. The answers t o thesequestions are t o he found hv activelv readine the chaoter surveys and n o t q carefullv the specific compounds rhosen for dernmstration. The furmer is based on the breadth of knowledge of organic syntheses and a vital sense of what types of conversions are apt t o be desirable. The latter is based on a realistic understanding that the general method must be used to prepare specific difficulty obtainable eompounds if the method is to achieve any currency. It is no accident for example, that P. 158 provides a stereospecifie synthesis of the thermadynamieally less favored trans-l-hydrindanone from vinyl cyclohexene. The third "concurrent" b w k provides insights into organic laboratory experimentation from one of the most successful lahoratories in the world. Early in my chemical career I became painfully aware of the truth of the expression "any pair of hands can mix reagents hut only s chemist can get the desired compound out of the reaction mixture in good yield and high purity." What one learns in going from "a pair of hands" to "a chemist" is the ineredihle attention that is required during "workup." There are few better teachers of this difficult, though critical part of organic chemistry, than Professor H. C. Brown. This book captures much of thatinvaluable teaching, and abounds with examples of this kind of attention of detail that leads to good results. Among the many eaamples, note 4 on page 187, is representative even though tetrahydrofaron and the product boil approximately 50°C apart, careful fractionation is required t o obtain a pure product.'' This is a hook that can and should be read in different ways. From the upper Level undergraduate t o the busy professor i t will provide value. Shelton Bank State Univemily of New York at Albany Albany. 12222
Creatfvity In Organlc Synthesis. Volume 1
Josjit S. Bindra and R a j a Bindra, Pfizer.. Ine.. Graton. Connecticut. Academie Press, Inc., New Ymk, 19'5. xiv 322 pp. Flow Charts. 24 X 19 cm. S11.50.
.
+
This is a collection of synthetic routes to more than 67 natural products selected from the literature from mid-1969 to mid1974. Each compound or group of related compounds is covered as a separate section including a hrief description of the eompound, its source, any unusual characteristics, and a few comments on the strategy or more unique steps in the synthesis. This is followed by a flow chart showing the reagents and intermediates in each step ledding t o the product, and also the percent yield for about half of the steps. Thwe who are familiar with "Art in Organic Synthesis" hy N. Anand,.J. S. Bindm, and S. Rangmathan, Holden-Day, Inc., San Francisco, 1970, will recognize this format. The present baok continues in the literature where the fir@ finished. The structures and type are larger and more attractive in the new book, and the coverage has been narrowed. excludine the still verv active area of rynthezis of unnnturnl compounds wrth high strain o r geumetrml interest Anyone involved in synthesis of complex molecules will find this a valuable resource. I t can be scanned far more rapidly than journal accounts t o learn strategy or notice applications of many new selective reagents. I t is also a concentrated source of examples suitable for study in a course in advanced synthesis. The inevitable small errors will be no problem for most readers; for example the iodolactonization (p. 211) was actually carried out with NaI 12. The reducing agent on p. 117 is actually sodium bis(2-metboxyethoxy) aluminum hydride. Disiamyl borane 1s incorrectly formulated on p. 154, and 1-hromo-3-methyl-2-butene is shown as a higher homolog on p. 106. This book is a unique source for rapid scanning of synthetic routes and would be of interest t o most chemists practicing or studvine .. advanced svnthesis. I t is. hawever, a selectiun of c&s and shouldnut be considered as a review or an indication uf the overall scope of modern synthesis. , ~
~
+
.
John C. Stowell Unlverrlty of New Orleans New Orleans. Louisiana
\
Topics In Nonbenzenold Aromatlc Chemistry. Volume 1 Edited by Tetsuo Nome, Tohoku University, Ronald Breslow, Columbia University, Sho Ito, Tohoku University, Klaus Hafner, Teehnische Hochshule Darmstadt, and Ichiro Murofo, Osaka University. John Wiley and Sons, New York, 1973.295 + pp. Figs. and tables. 23 X 15.5 em. $21.50. If the potential buyer is concerned that this baok will simply be a rehash of the
