Organometallics, Vol. 1, No. 11, 1982 1555
Book Reviews Gmelin Handbook of Inorganic Chemistry, 8th Edition, Se, Selenium. Supplement Volume B1, Compounds with Hydrogen, Oxygen, Nitrogen. W. Behrendt and U. W. Gerwarth, volume authors, H. Hein, D. Doschel, P. Kuhn, B. v. Tschirschnitz-Geibler, volume editors. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin/Heidelberg/New York. 1981. IX + 343 pages. DM 933. $434.40. This volume represents an updating of the first volume, “Selen” B which appeared in 1949 and covered the literature through 1947. This supplemental tome covers the literature which describes the hydrogen, oxygen, and nitrogen compounds of selenium published from 1948 through mid-1980. The first page informs the reader of the existing general literature which covers the topic covered by this book. Section 2.1 covers the HSe and DSe radicals and present.9 a detailed coverage of their spectral properties. Section 2.2 is concerned with H,Se and its isotopic species. Among the various topics covered are its preparation, thermodynamics, toxicity, structure, details on its vibrational spectrum, NMR, both ‘H and 77Se,and optical spectra. Its chemical reactions, both organic and inorganic, are covered. Section 3 describes the binary oxides, SeO, SeOz and SeO* Descriptions of the spectral properties of the three species are given. The mechanical and thermal properties of the di- and trioxides are presented. Their chemical behavior is described briefly, but thoroughly and includes inorganic, organic, and organometallic reactions. Section 3.2 covers the oxoacids of selenium and their anions. Although the spectroscopic properties are included, the greater coverage, as expeded, is devoted to their chemical behavior. Besides the well-known acids, H2Se03and H2Se04,the following are also given thorough treatment: (H2Se03)2,H2Se205,HzSe05, HzSe208, H2Se207, HzSe3010,and H4Se3011. The interested investigator will find, among other topics, the following: detailed spectroscopic information, physical properties, and chemical behavior in both aqueous and nonaqueous media. Section 4 is concerned with selenium-nitrogen compounds. The first species covered is the SeN radical. This is followed by coverage of, Se4N4,a molecule of considerable current interest. The final four sections deal with nitrosyl and nitryl selenates, selenious and selenic acid diamides, polymeric anions of selenonylimide, and anions of imidoselenic acids. The volume contains a wealth of useful information. Interest in this element has grown dramatically during the past 10 years with a concurrent explosion in the related number of publications. Hence, although the coverage of particular topics is very brief in some instances, the literature coverage is detailed and thorough. Ralph A. Zingaro, Texas A&M University
Sulfur in Organic and Inorganic Chemistry. Volume 4. Edited by A. Senning. Marcel Dekker, Inc., New York. 1982. xii + 440 pages. $75.00. The first three volumes of this series appeared approximately 10 years ago, and the present book brings an update of Volume 1 (with the exception of the original chapters on the S-S and the S-0 bond). Included in Volume 4 are chapters on the S-Si bond (A. Haas and R. Hitze), the S-N bond, (H. W. Roesky), the S-P bond (L. Almasi), the S-F bond (J.M. Shreeve), the S-C1 bond, (W. R. Hardstaff and R. F. Langler), the S-Br bond (P. S. Magee), and the S-I bond (L. Field and C. M. Lukehart). Both inorganic and organic sulfur chemistry have seen considerable progress in the last 10 years, so this update is appropriate. It is unfortunate that chapters on the S-S and S-0 bonds could not be included in the present volume. The discussion of the S-Si bond, short though it is (13 pages, 36 references), is useful to have since organosilicon compounds, including sulfur derivatives, are finding ever increasing utility in organic synthesis. The current interest in S-N compounds, in part a result of the interesting properties of (SN),, is high, and the 31-page (138 references) chapter on this subject will be useful to workers in this field. The chapter on the P-S bond, with its 490 references, is much longer (84 pages) and brings results mostly from the area of organophosphorus chemistry. The focus of each sulfur-halogen chapter is quite unique, reflecting the nature of the S-X species involved in each case and the emphasis of the research which has been done. The chapter
on S-F chemistry is full of interesting exotica, in large part because of the facility with which S-F compounds are formed in which sulfur is in a higher oxidation state. This excellent 61-page report on this very active area by one of its leading contributors is backed up by 481 references. The 89-page chapter on the S-C1 bond is divided into two parts: discussions of the chlorination (by C1, and S02C12,for the most part) of organosulfur compounds, reactions which produce organosulfur derivatives with S-Cl bonds, and of inorganic S-Cl compounds. The discussions in the 43-page S-Br chapter are organized throughout according to compound type, f i t inorganic compounds and then organic compounds. The S-I compounds which are stable are rather limited, so the organization of the 41-page S-I chapter is different again. A discussion of the donor-acceptor complexes formed between I2 and IX and sulfur compounds is included, along with sections on inorganic S-I compounds and organic sulfenyl, sulfinyl, and sulfonyl iodides. All chapters cover the period of 1969-1979 and they present useful, comprehensive discussions which are well referenced. There is an author index for the references cited in the book, and there is also a subject index. The contents of the previous three volumes are listed. Together with its three companion volumes, the present book may be recommended as a useful source of information on sulfur chemistry. Dietmar Seyferth, Massachusetts Institute of Technology
13C NMR Data for Organometallic Compounds. By B. E. Mann and B. F. Taylor. Academic Press, New York. 1981. viii 326 pages. $32.50.
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This book is a volume of the excellent “Organometallic Chemistry” series of monographs, edited by P. M. Maitlis, F. G. A. Stone, and R. West. As the authors point out, the 13C chemical shift range for organometallic compounds spans dc -61.7 to +448.3. Within this range lie many compounds, main-group and transition-metal derivatives, whose 13CNMR spectra have been measured. The authors list these chemical shifta and associated spin-spin coupling constants in 19 tables which take up 222 pages of the book. The organization is by ligand type and, within a given ligand-type table, by element. Compounds of the metalloids (B, Si, Ge, As) and even of phosphorus and selenium are included. The literature (1799 references) is covered through the end of 1979. The first 36 pages of the book are used to present “A Guide to the Use of 13CNh4R Spectroscopyto Investigate Organometallic Compounds”. Included here are, inter alia, useful discussions of the chemical shift range, coupling to quadrupolar nuclei, theoretical treatments, empirical relationships, correlations with other experimental parameters, 13C spin-spin coupling, relaxation measurements, and applications. These discussions are based on the reasonable assumption that the reader has some familiarity with the experimental and the organic aspects of 13C NMR spectroscopy. Although the book is a photoreproduction of the original manuscript, the final result is completely legible and attractive. The only feature which could be considered objectionable is the I display of cyclic formulas in linear fashion, e.g., Co(C5H5)(CO)OC(OR)=C(C02R)C0. The saving in space leads to a loss in clarity. This very useful book should find a place in all chemical libraries; the price is not prohibitive for the individual purchaser. One hopes that future editions will keep this book up-to-date. Dietmar Seyferth, Massachusetts Institute of Technology
Progress in Inorganic Chemistry, Vol. 29. Edited by Stephen J. Lippard. Wiley-Interscience, New York/Chichester/Brisbane/Toronto/Singapore. 1982. v + 401 pages including Cumulative Index, Volumes 1-29. ISBN 0-471-09370-X. $49.50. This volume continues the high standards characteristic of the previous members of the series and consists of five chapters convering diverse topics. The first by M. H. Chisholm and I. P. Rothwell deals with chemical reactions of metal-metal bonded complexes of the transition elements. As stated by the authors, this chapter is not intended as a comprehensive account but rather is an illustration of emerging trends in research in this area.
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
