book reviews Halonlum Ions

Arizona 8572 1. Janos H Fendler and Eleanor J Fen-. E. W. Anacker. Montana State University. Bozemn, Montana 59715 dle~, Terai A & M University. Acade...
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Halonlum Ions

George A. Oloh, Case Western Reserve Universitv. John Wilev & Sons. New York, 19%. xiii + 1 9 0 p c Figs. and tables. 16 X 23.5 cm. $18.50. Dynamlc Nuclear Magnetlc Resonance Spectroscopy Edited byLloyd M. Jackman, The Pennsylvania State University, and F. A. Cotton, Texas A & M University. Academic Press, New York, 1975. xiv 660 pps. Figs. and tables. 15.5 X 23.5 cm. $48.

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Since 1951, one of the major uses of nuclear magnetic resonance (nmr) spectroscopy has been for the study of various exchange processes with half-lives in the ranee lo-' to basis for these techniques is discussed in this book's first five chapters, which are fallowed by ten chapters reviewihg applications to particular types of exchange processes. Readers unfamiliar with current mathematical terminolopv will have difficultv with the ~., first five rhnprm (hecoming l h r in "ord~nnry Hilbert spaw" and "l.iw\illr rparr"); forrunatply, thorough understanding of the theory is not required for appreciation of the applications. Most chemists will be interested in a t least one of the 15 chapters: Time-Dependent Magnetic Perturbation (H. S. Gutowsky); Deliniation of Nuclear Exchange Processes (W. G. Klemperer); Band-Shape Analysis (Gerhard Binseh); Application of Nonselective Pulsed NMR Experiments-Diffusion and Chemical Exchange (L. W. Reeves); Determination of Spin-Spin Relaxation Times in High-Resolution nmr (Ray Freeman and H. D. W. Hill); Rotation About Single Bonds in Organic Molecules (S. Sternhell); Rotation About Partial Double Bands in Organic Molecules (L. M. Jaekman); Dynamic Molecular Processes in Inorganic and Organometallic Compounds (J. P. Jesson and E. L. Muetterties); Stereochemically Nonrigid Metal Chelate Complexes (R. H. Holm); Stereochemical Nonrigidity in Organometallic Compounds (F. A. Cotton); Fluxional Allyl Complexes (K. Vrieze); Stereochemical Nonrigidity in Metal Carhanyl Compounds (R. D. Adams and F. A. Cotton); Dynamic NMR Studies of Carbonium Ion Rearrangements (L. A. Telkowski and M. Saunders); Conformatianal Processes in Rings (F. A. L. and Ragini Anet); and Proton Transfer Processes (Ernest Grunwald and Earle K.Ralph). With almost 2000 references, this is by far themost comprehensive work on the subjed The authors of each chapter are top workers in the field. The illustrations are very clearly and attractivelv, oresented. However. the p r m i~ SO high that most vhemms will refer tu the hook from their insritur~onnlrather than their personal library.

This hook is the latest volume in the wellreceived series entitled "Reactive Intermediates in Organic Chemistry," edited by G. A. Olah. This series is intended to provide a critical discussion of the formation. isolation. phyirnl rhnmrterizntion, and reactions of ~ h rimportant intcrrnedinrm of organic chemistry. Previous volumes have covered carbonium ions, radical ions, nitrenes, carbenes, and free radicals. The book surveys the current state of research on organic halogen cations, that is, positive halogen ions having two bonds t o carbon. Such ions have long been postulated as transient intermediates in organic reactions, such as the addition of halogens to alkenes. Diaryliodonium ions are considerably more stable and have been known for many years. The coverage in this book is primarily restricted to long-lived halonium ions, either as isolated salts in the case of diarylhalonium ions, or in solution in nonnucleophilic solvents a t low temperatures in the ease of dialkyl and arylalkylhalonium ions. Major topics include methods for the preparation of halonium ions and an extensive discussion of the structure of the ions based on spectroscopic studies, especially proton and carbon magnetic resonance studies. The chemistry of halonium ions is also presented, including discussions of phenylation reactions with diphenylhalonium ions, halonium ylides, and the role of halonium ions in the Friedel-Crafts reaction and in the addition of halogens to alkenes and alkynes. Recent observations of halogen cations with one carbon ligand and one hydrogen ligand are also briefly discussed. The hook is written in a concise and readable style by one of the leading experts in the field. Unfortunately, it is marred by a large number of misprints. While the majority of these are obvious, a few are quite confusing. For example, the structure a t the top of page 135 should be 4-chloro-4-penten-l-yl trifluoroacetate rather than the 5-chloro isomer shown. Over 204 papers from the chemical literature are referenced, a few from as late as l97i. Aimed towards thotc engaged in re. -earth in this field, thls h m k should find n valuable place in their libraries

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Joseph M. Harnoack Unwersdy 01 Denver Denver. Colorado 80210

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Robem 6. Bates University of Arizona Tucson. Arizona 8572 1

Catalysls In Mlcellar and Macromolecular Systems Janos H Fendler and Eleanor J Fend l e ~Terai , A & M University. Academic I're;~, Yew Ywk, 1975 xii T 545 pp. Figs. and tables. 15.5 X 23.5 rm. $44. Since considerable research in recent years has been concerned with elucidating the ability of surfactants and various macromo-

A60 / Journal of Chemical Education

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lecular substances to influence the rates, uroducts. and stereochemistrv of a number u t reactions important for academicand indwtrial reasun;, Jamb and Eltanor Fcndler'., "mmmugraph on the wtdl>se, elicited by aqueous and nonaqueous micelles, synthetic and naturally occurring polymers, and phase-transfer eatalysts"is both timely and welcome. The treatment is intended to provide "euidanee and stimulus to biooreanie. ,. . inurgan~r,pharmareutiral, cdloid, phyriral, and pc,lvmer rhemisti as d l as t t r t h t w whu seek novel and unique catalysts in industrial processes." For each catalytic system considered, the Fendlers have tried t o tailor the length and detail of their discussion to fit the need, as judged from the availability of recently published summaries and reviews. Surfactants and micellar catalysis accordingly occupy about three-fourths of the book. In the first three chapters, the authors discuss the preparation and purification of surfactants, the physical and chemical properties of surfactants and micelles in aaueous solution. and solubilizatian in aquemr mirellnr solurmns. Since relattvely m m t rcviewiareaveilahle in these a r e s , the discussions are brief. The authors next treat the principles of micellar catalysis in aqueous solution and follow with details of the effects of micellization on reactivity in a number of reactions. Thev conclude their discussion of surfactants ulr h review; id ratalvi~shy rweraed mirelles ~n nmnqueous solvents nnd entnlyris in Ilq"id, crystalline, and ternary systems. In the final chapter, the authors discuss reactions a t interfaces, in cavities of crown ethers, in the presence of polymers, and reactions catalyzed by quaternary ammonium and phosphonium cations. An important feature of the book is the extensive use of tables. The authors have attempted "to tabulate the available data, to June, 1974,exhaustively." Sinceover 40%of this 545-page volume is comprised of factual and well referenced tables, their efforts appear to have been successful. Relevant papers published on micellar and macromolecular systems after completion of the manuscript and up to December, 1974, are summarized in an addendum. The hook is a treasury of information and should he invaluable to investigators either working or planning to enter the field. It should be a valuable reference for graduate courses in catalysis, hut its coverage is too narrow to recommend its use as a general text. Like most comparable efforts, this one cm~taimemeerrorJ. l.ictin{: suhutrate residencetimt..i in t h ~tmirrll~a. 10" and 10"sec imtend uf 111'" and 10-' ser r p n p 441 and omitting a set of parentheses and micellar charge from eqn. (2.11) are examples of errors that will not create serious problems far the reader. However, errors such as found in eqn. (2.13) (last term is incorrect) and on page 69 and 70 (rotational correlation times are regarded as rotational frequencies of tumbling) can be distressing.

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E. W. Anacker

Montana State University Bozemn, Montana 59715

(Continued on page A62)