1556 Organometallics, Vol. I , No. 11, 1982 Following introductory remarks on the electronic structures of metal-metal bonded complexes insofar as they are presently known the chemistry is discussed by reaction type, viz.reactions forming metal-metal bonds and reactions which change and which do not change the metal-metal bond order. In the last the emphasis is on reactions which differ from those of mononuclear complexes because of the presence of additional metal centers. Also treated briefly are fluxional processes and catalytic systems. The review provides good coverage of the various types of systems known and provides a suitable starting point for persons interested in entering this area of research. It is also reasonably current as it contains a fair number of references appearing within the last 18 months. One minor drawback is the running title which seems to imply the subject is restricted to reactions of the metal-metal bond itself. Following is a very thorough and up-to-date coverage of the chemistry and structures of rhodium(I1) complexes by T. R. Felthouse. Although not limited to dimeric complexes, the majority of the coverage is of the dimers since so few authentic monomeric Rh(I1) complexes are known. Besides details of their preparation and reactions, the occurrence of Rh(I1) complexes in catalytic and bioinorganic systems is reviewed. Finally spectroscopic studies including extensive EPR data and a discussion of the controversy (now resolved) over the metal-metal bond order in the dimeric carboxylate complexes are presented. The third contribution by K. Seppelt and D. Lentz provides a brief account of novel developments in noble-gas chemistry, but with the exception of some recent contributions from the author’s laboratory most of the references are a t least 2-years old. The majority of the coverage is limited to accounts of structural studies on XeFs and the use of noble-gas compounds as oxidants or fluorinators for main-group compounds. Although somewhat fragmentary and limited in scope, this chapter does provide an entry to the literature for this area. The remainder of the volume consists of two reviews, one on recent advances in the theory and experimental techniques of magnetochemistry by C. J. O’Connor and one on NMR spectroscopy of metal nuclides by J. J. Dechter. Both cover the recent literature (particularly the second which includes only the period 1978-October 1980) and focus on recent results while highlighting current directions in research in both areas. Following descriptions of the advantages and limitations of the experimental methods available, summaries of the theoretical bases of the two areas are presented. While the practitioner probably will find these satisfactory, those less familiar with the theory will need to also consult more extensive sources. The O’Connor article ends with recent results on current problems including the magnetic properties of polynuclear clusters and low-dimensional materials, magnetic phase transitions, and applications of magnetochemical techniques to biochemical systems. The final portion of the Dechter article presents results of NMR measurements on metallic elements from groups 1A-5A with the majority being on the alkali metals. Generally the coverage of both these articles appears thorough. Joel T. Mague, Tulane University
Asymmetric Reactions and Processes in Chemistry. Edited by E. L. Eliel and S. Otsuka. ACS Symposium Series No. 185. American Chemical Society, Washington, D. C. 1982. xiii + 300 pages. $31.95. This book contains 18 major lectures and 9 short communications presented in a joint U.S.-Japan Seminar on the topic of asymmetric reactions and processes held at Stanford University, July 7-11,1981. Although a few notable omissions are apparent, such as H. C. Brown’s asymmetric hydroboration and K. B. Sharpless’ asymmetric epoxidation (presented in the meeting but not included in this book), this seminar well represents recent pioneering activities in the field and provides an excellent overview of the current trends in asymmetric organic synthesis. Several papers describe highly enantioselective syntheses in-
Book Reviews volving chiral main-group organometallics. These include papers by Mukaiyama, Eliel, Koga, Meyers, and Posner. Although these papers are dominated by the use of Li and Mg, that of Zn, B, Al, and a transition metal Cu is also noteworthy. Two papers, one by Heathcock and the other by Nozaki, deal with diastereoselection in the aldol reaction and allylation of carbonyl compounds, respectively. The paper by Heathcock represents an excellent introduction to the concept of “double stereodifferentiation”. These papers are followed by several discussions of the use of chiral phosphine transition-metal catalysts containing Rh, Ni, and Pd. Although catalytic hydrogenation (Ojima, Saucy, and Harada) dominates these papers, the Pd- or Ni-catalyzed asymmetric cross coupling (Hayashi) and the Rh-catalyzed isomerization of allylamines (Otsuka) point to some new trends in this area. Although largely unrelated to organometallic chemistry, papers on the use of immobilized enzymes in asymmetric synthesis (Chibata and Whitesides), biomimetic asymmetric reduction (Ohno), and biological one-carbon-transfer reactions (Floss) as well as a discussion of more classical asymmetric synthetic methods by Trost and that of the use of a chiral HPLC stationary phase by Pirkle provide stimulating readings. In summary, this book should prove to be informative and useful to all chemists, organic, organometallic, or inorganic, who are interested in asymmetric organic synthesis. Ei-ichi Negishi, Purdue university
Houben-Weyl Methoden der Organischen Chemie, 4th Edition. Volume IV/la. Oxidation,Part I. Edited by H. Kropf. Georg Thieme Verlag, Stuttgart. 1981. xxxi + 1405 pp. DM 1250. This is Part I of a two-part series on oxidation. With this work the four-book set (1VIla-d) of the 4th edition covering oxidation and reduction in organic chemistry is now complete. Part II,which appeared in 1975, deals largely with metallic oxidants derived from transition metals, main-group metals, and lanthanides. An obvious, but noteworthy feature of such metallic oxidants is that they are invariably compounds of the metal with one or more of the highly electronegative main-group elements found in the upper right-hand corner of the Periodic Table. Metallic oxidants are extremely useful because of the marvelous selectivity they often exhibit, but it is the electronegative elements to which they are bound which render them oxidants in the first place. Therefore, it is appropriate that Part I concentrates on oxidations in which the electronegative elements themselves are the primary actors. The work begins fittingly with chapters on the earth’s most famous oxidants-molecular oxygen and ozone. It then moves on to peroxides, sulfur, and selenium compounds, halogen compounds, nitrogen compounds, other pnictogen compounds, and finally biochemical oxidations. The thoroughness that one has come to expect of this famous series is apparent throughout. Even in areas which I know especially well (such as selenium oxidations and metal-catalyzed peroxide oxidations), I ran across interesting reactions that were new to me. The weakest aspect of many works on organic oxidations is in the area dealing with reaction mechanisms (a notable exception to this trend is the recent book by R. A. Sheldon and J. K. Kochi, ”Metal-Catalyzed Oxidations of Organic Compounds”, Academic Press, New York, 1981). The present work, as is customary in Houben-Weyl, emphasizes synthetic transformations and wisely keeps a low profile on the often thorny subject of oxidation mechanisms. In works of this magnitude errors inevitably creep in. I will only call attention to one important correction concerning work from my laboratory. The data presented in Table 5 on page 234 contains numerous errors. For the corrected results see reference 1 (and references cited therein) on page 233. I can be very enthusiastic about the overall quality of this work. Access to this and the other three books (Volume IV) of this redox series will be of great value to anyone interested in organic functional group manipulation. K. Barry Sharpless, Massachusetts Institute of Technology
