Coordination Compounds
Dean F. Ma~tin,University of Illinois, Urbana, and Barbara Maytin. McGraw-Hill Book Co., Inc., New York, 1964. vii 90 pp. Figs. and tables. 14 X 21 cm. $4.95; paperbound, $1.95.
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This is another in the increasing liat of books available for supplementing the usual freshman chemistry course. The authors have not attempted ta be all-inclusive but hsve attempted to indicste the areas of importance in coordination chemistry. The book consists of five chapters: The World of Coordination Compounds, The Years of Discovery, The Architecture of Coordination Compounds, The Y e m of Understanding and Coordination Compounds in Solution. The best of these from the supplementary viewpoint is the second. In this the development of the chemistry of coordination compaunds is discussed, beginning with dyes and pigments continuing through the early ideas of coordination chemistrv and finsllv a lone section
The other four chapters allow more space for discussion of their topics than is usually found in an introductory college chemistry text but the level of discussion is usually about the same. This impression was confirmed by a student who had been exposed to T. L. Brown's text and the qualitative analysis text of E. J. King. The explanations given are usually clear and adequate, although there are a few occasions when definitions have been delayed a few pages beyond the optimum point. The authors have used diagrams freely, usually successfully. There are a few instances here also where a. more complete diagram might hsve been given earher ret,her than in the position in which it does appear. To consider each of the chapters in turn, the World of Coordination Compounds is essentially a, chapter of definitions and examples. I t includes alro some factors that influence the formation of coordiiation compounds such as the size of the metal ion, the structure of the ligrtnd, chelsting possibilities, and steric requirements. There is also a. short section on nomenclature and a section on the uses of coordination compounds. The Architecture of Coordination Compounds includes considerable discussion of isomerism, including optical isomerism, which is nicely illustrated with some line drawings of a schematic polsrimeter. The different coordination numbers and the geometries expected from them are described, and brief reference is msde to the implications of this structure. The Years of Understanding covers the theoretical material including reaction mechanisms, isomer number methods for determining structures, and physical methods, but only mentions such things as absorption spectra, exchange reactions, and resonance techniques. The theory presented includes a very brief summary of the early WernerLewis-Sidgwiek theories, Paulingk contribution, and two pages of ligand field theory. Finally, Coordination Com-
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pounds in Solution treats equilibrium data and the stepwise formation of complexes, the factors which affect the form* tion constants, and a short section on reactions in solution. A final appendix includes patterns far the preparation of paper models of a tetrahedron and an octahedron. The student who reads this book will be introduced to a large number of topics but will feel that he controls only a ver,v few. Since this was the intention of the book, the authors have reached their goal. The list of references a t the end of each c h p t e r is selective and quite varied. In some cases the student will be unable t o locate these unless he has a very complete library, but in others he should find that they are easily available. Perhaps a reviewer should not quarrel with the authors' decision to limit their subject in their own way, but it does seem as if the book would be of more use to moat students if some of the topics which are barely mentioned (usually in the form of "These have been considered in detail by other authors" with a reference) had been treated in s. bit mare detail. This undoubtedly would have increased the book beyond its present ninety pages of text but would have msde it more truly a supplement rather than a duplicate of the material covered in a fairly large number of freshman texts. DONALD A. TARE College of Wooster Woostw, Ohio
Atomic Structure and Chemical Bonding
F. Seel, University of Saarbriicken. Translated by N. N. Greenwood and H. P . Stadlet, both of King's College, Newcastle upon Tyne. John Wiley and Sons, Inc., New York, 1963. vii 112 pp. Figs. and tables. 13 X 19 cm. $2.10.
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Professor Fritz Seel's book, "Atombau and Chemische BindungNwas first published in 1956 and was meant to give a concise, non-mathematical account of the modern theories of chemical bonding to students who have had little previous training in this area. In the reviewer's opinion it succeeds in this purpose. Judging from the general readability of the book, the translators, Greenwood and Stsdler, have done an excellent job. There are few errors of any importance and the diagrams are clear, concise and understandable. The treatment of chemical bonding is conducted according to four basic types: ionic, covalent, metallic and intermoleeuLar and emphasis ia given to the unity of application to the basic fields of chemistry. The strength of this book lies in the skillful use of pictorial diagrams and models to explain in a nonmathematicsl manner conclusions reached through quantum-mechanical calculations. Thus, it is well suited for supplementary resding to upper level undergraduate or beginning graduate students. Some of the more recent concepts such as ligand field theory and charge transfer complexes have been introduoed and there is an interesting
discussion of chemical reactivity as related to mode of bonding. Pest I of the book (first four chapters) deals with electronic distribution, the shape of orbitals, and describes how the periodic table can be built up from the structure of atoms. Part 2 contains discussions of the geometry and formation of ionic lattices, covalent bonds, bybridisation, multiple bonds, stereochemistry, metallic and intermetallic bonding, iondipole, and dipole bonding and dispersion forces. Included also is a description of the relationships between chemical bonding and some physical properties such as: reactivity, mechanicel strength and color. Because of the book's short length, many interesting aspects of bonding have been omitted but the topics covered have been well selected and are introduced in such a manner that they will stimulate the reader to further study using the bibliography provided.
R. KENTMURMANN University of Missouri Columbia VoIaYle Silicon Compounds
E. A. V.EbswortA, University Chemical Laboratory, Cambridge, England. Macmillan Co. (a Pergamon Press 179 pp. book), New York, 1963. v Figs. and tables. 16 X 23.5 em. $7.50.
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It has become de rigueur nowadays that any hook or monograph dealing with silicon chemistry be prefaced with the story resurrecting old Professor Kipping of Nottingham and his unfortunate prediotion concerning the uselessness of silicon materials. (Your reviewer enters a plea of guilty with the rest.) Dr. Ebsworth has skilfully managed to avoid this particular pitfall and his "Volatile Silicon Compounds" goes from strength to strength. Only the title is misleading: little that is known of germanium and tin Byatems seems left out and the volatility of Si4, bis-(triethylsily1)sulfide or silyl potassium is arguable. Best not to quibble over a bargain, however, and interesting comparisons result when these compounds are included. The book begins by discussing the atomic properties of silicon and its cogenera in the fourth group, and then takes up the compounds formed with hydrogen and members of Groups IV, V, VI, and VII, concluding with a miscellany of silicon bonded to pseudo-halogens, boron, transition elements, and alkali metals. In taking up these topics the author reminds us constantly of the contrast between the current state of knowledge and what needs to be known to achieve understanding, with the result that there are sufficient research suggestions strewn through the pages to maintain a large institute on a round-thaclock 24 hours per day. During the last decade it has become increasingly evident that the concept of hack bonding between lone pair electrons on atoms adjacent to silicon and empty 3&orbitals of the silicon atom is quite useful in explainingmany of the differences between silicon compaunds and their carbon analogues. The formation of these d)&onds, as the author's notation (p
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has it, has been justified theoretically and the explanation readily lends itself for use in discussing systems where silicon is bonded to nitrogen, oxygen and the h a b gens, and is invoked to explain nearly all the differences in structure and reactivity between organic compounds and their analogues containing other elements of the fourth group. It is, therefore, an apprw priate time to prtU8e and take stock. Thk exercise runs as a thread of argument through the entire book and marks perhaps its leading feature. Dr. Ebsworth has produced s, highly critical compilation of the wide variety of phyaicel rtnd chemical evidence now available and he draws wise and careful conclusions concerning the limitations of its application. The approach throughout is from the modern physico-chemical viewpoint and much space is devoted to the resulta of spectroscopic studies, especially NMR. Again judicious use is made of the data, and the author is continually a t pains to point out the limitations of the methoda as with the relative values of the proton chemical shifts in methane and silane. Along the way we are treated to the concept of the "Scandanide Contn~etiau,"a clever construct helpful in rationalizing the relatively small change in covalent radius between silicon and germanium, and perhaps a cause of the alternating electronegativity found in the fourth group as well. Certainly s. great handicap in summarizing present knowledge in 80 active a field is that conclusions drawn in the manuscript will be dated by new work by the time of publication, and West's stable silieonium ion (C&EI\', Dee. 30, 1963) may be only the first case in point. But the effect is surely less the more cogent the analysis, and Dr. Ehsworth has distilled into 163 pages an extremely well-thought out and highly critical reexamination of the physical and chemical evidence available on these interesting systems. I t is important to point out in conclusion that "Volatile Silicon Compounds" complementa Professor Eaborn's "Organosilicon Compounds'' 11960), but stands separately from it and should certainly be of interest to anyone who finds this latter workuseful.
Chemistry in Nonoqueour Ionizing Solvents. Volume 4, Chemistry in Lower Fatty Acids and Derivatives
Edited by Gerhart Jander, Hans Spand m , and C. C. Addisa. Interscience Publishers ( a division of John Wiley and Sons, Inc.), New York, 1963. xv 313 pp. Figs. and tables. 17 X 24.5 cm. $12.
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Properties of solutions in nonaqueous solvents have been studied since the beginning of this century and there is now an abundant literature on this subject which is both of academic interest and of
originated dy the late G. ~ & e r and by H. Spandm, in which our present knowledge
is presented concisely, is a timely and welcome addition to the literature. The volume under review deals with acetic acid, formie acid and some of their derivatives, acetic anhydride, acetamide, formamide and substituted amides. All ehaptern are in German, except the last section on amides, which is in English. The most extensive treatment in 129 pttges is that of acetic acid by K. Heymann and H. Klaus. Exteneive discussions with tables and figures are given of the following topics: physical properties, purification, solubility of inorganic and organic compounds, conductance, viscosity, transference numbers and ion mobility, potentiometry, acidity function, autoprotolysis constant, aeid-base equilibria and titrations, polarography, cryoseopy and solvalysis. This is the most complete review availilable on this subject. Although reference is made to a paper by Higuchi el al. (1956) it is regrettable that the formation constants of their set of indicrttors are not listed in a table. Also, neither photometric (e.g., the ingenious method of Higuchi, Rehm and Barnstein, Anal. Chem., 28, 1506 I19561 is not mentioned) nor thermometric end point determinations are reported. In general, the same order of treatment is maintained in the chapters dealing with acetio anhydride (69 pages) by H. Surawski, with acetamide (20 pages) by G. Winkler, and with formic acid (28 pages) by H. Knauer. It is unfortunate that the more recent studies by A. Popov and J. Marshall in formic acid are not included. The last part (30 pages) deals with formilmide and derivatives of amides by the well known expert L. R. Dttwson. An excellent review of conductance, ion mobilities, solubility and degree of dissociation is presented. Unfortunately, hardly anything is said about acid-base properties of the solvents and acid-base equilibria and titrations. Also the literature on polarography in these solvents is not reviewed. A subject index of 24 pages concludes this book. Although in some chapters s. more critical discussion, especidly of the older literature, might have been desirable, the authors deserve our gratitude for having made available a wealth of systematically presented information. The book, which undoubtedly will stimulate many readers to pursue further research in nonaqueous solvents, can be recommended without reservation.
and rendered into the ten languages. Unfortunately the latest standards are not used ("C, Kr light, etc.) for the defitions. A second extensive table lists the national units for 69 countries and gives conversion factors to the US., U.K. and metric systems. Lists of defining words (absolute, reciprocal, etc.) and prefixes (tera to pico) are also translated into the ten languages. Two complete indexes, one for Russian only, are provided.
W. F. K. Naturally Occurring Oxygen Ring Compounds
F. M. Dean, University of Liverpool, England. Butterworths, London, 1963. 661 pp. Figs. and tables. viii 16 X 25.5 cm. $24.95.
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Among the nrtturdly occurring heterocycles, which constitute one-half of all natural products, oxygen heterocycles are fewer in number than the nitrogencontaining heteroeyoles and have received less attention in surveys both of natural products and of heterocycles. This book renreaents the first a t t e m ~ to t deal svstematically with the extensive chemistry of these oxygen heterocycles. Fifteen chaptera me concerned with the common classes of five- and six-membered oxygen heterocycles, such as furans, benzofurans, pyrans, unsaturated lactones, coumarins, chromans, chromens, chromonea, chromanones, xanthones, and flavonoid compounds. Two chapters deal with rings of other sizes, rings with two oxygen atoms, and compounds containing two fused oaygen-containing rings. Not all naturally occurring oxygen heterocycles are included: saturated bctones, 1,3benzodioxoles (i.e., derivatives of methyleuedioxybenzene), cyclic hemiscetds and hemiketals (e.g., carbohydrates), and compounds with rings containing both oxygen and nitrogen atoms have been arbitrarily excluded. The compounds discussed me almost exclusively of plant origin since only a. few oxygen ring eompounds have been found in animda. For each chss of compound, a general description of the structural characteristics and chemical properties is given, followed by a eatslog of specific compounds. For each of the latter there are presented the ocI. M. KOLTHOFP currence, synthesis, proof of structure, and, Uniuwaity of Minnesota often, biological properties. The find Minneapolk chapter is an excellent survey of biosynthesis of oxygen-contsining compounds. Although the emphasis is on oxygen ring Lexicon of International and National eompounda, numerous related types of Units compound me necessarily discussed, so that this chapter is of general interest as Compiled and arranged by W. E. an introduction to the theories of bioC h n , N. V. Philips Gloeilampensynthesis, the methods for determination fabricken, Eindhoven, Netherlands. of hiosynthetic pathways, and some of the American Elsevier Publishing Co., Inc., very convincing data which have been 76 pp. 13 X New York, 1964. vi obtained in support of hiosynthetic 19.5cm. 54.95. theories. Although the author states that his This book will be valuable for all who treatment of the field "is in no way exhave to translate units into or from the haustive, despite theinclusion of more than following languages: German, Spanish, two thousand references," the literature French, Italian, Dutch, Japanese, Polish, appears to be well covered through 1961. Portuguese, Russian, or Swedish. Three Some of the clmses of compounds discussed hundred terms are defined (in English)
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Vol. 41, No. 9, September 1964
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