Book Reviews of the truly broad synthetic methods. John J. Eisch, State University of New York a t Binghamton
Advances in Organometallic and Inorganic Polymer Science. Edited by C. E. Carraher (Wright State), J. E. Sheats (Rider College), and C. U. Pittman (University of Alabama). Marcel Dekker, New York. 1982. xii + 449 pages. $67.50. This volume is the fiist in a series of monographs that will give an overview of the research being conducted in the field of organometallic polymers. It was, however, somewhat disconcerting to notice that these papers originally appeared in the Journal of Macromolecular Science-Chemistry. The chapter on polymetallocenylenes by Neuse is an excellent review on the synthesis and characterization of poly-1,l’ferrocenylenes and their potential application and expected future developments. “Polymers for the Controlled Release of Organotin Toxin” by Subramanian and Somosekharen describe efforts to produce controlled release antifouling toxins from copolymers of tributyltin acrylate and acrylates, epoxies, urethanes, aziridines, and polyesters. An interesting chapter by Carraher et al. describes their studies on the identification of thermal degradation products of titanium polyethers using combined thermogravimetric analysis-mass spectrometry. Three chapters are devoted to the presentation of data on organometallic conducting polymers that have metal-like properties. Carlini and Sbrana review “Catalysis by Transition Metal Derivatives Bound to Structurally Ordered Polymers” with emphasis on examples where the characteristics of the polymer exert an influence on the heterogenized homogeneous catalysts. The chapter by Allcock e t al. on poly(difluorophosphazene) describes what appears to be a novel reagent for the preparation of a new class of poly(organophosphazenes) that possess substituents linked to the skeleton through direct phosphorus-carbon bonds. The chapter on “Metal Vapor Synthesis of Organometal Polymers and Polymer-Supported Metal Clusters” by fiancis and Ozin describes the generation of polymer-stabilized small metal clusters by the deposition of metal vapor into a fluid polymer and the interaction of vaporgenerated, small metal clusters with polymers. Overall the book serves&e purpose of providing reviews in the areas of Organometallic and Inorganic Polymers. The index appears to be fairly usefukirY accessing the data contained in this monograph. This volume should be of general interest to organometallic chemists. ; P. E. Garrou, Dow Chemical-New England Laboratory
Advances in Organometallic Chemistry. Volume 20. Edited by F. G. A. Stone and R. West. Academic Press, New York. 1980. ix + 369 pages. $56.00. This series is consistently excellent in the quality of the scientific reviews that it contains and the manner in which they are presented to the reader. Volume 20 continues in this tradition with a collection of six extensive and topical articles covering organometallic chemistry of main-group and transition elements. Each review is authored by chemists who are active researchers in the areas whereof they write. The first chapter (38 pages), by John A. Gladysz, deals with Transition Metal Formyl Complexes. The syntheses and reactions of these compounds are discussed in detail, and their relevance to catalytic reactions, particularly CO reduction, is emphasized. Key literature is covered through part of 1981, and an addendum provides a listing of notable additions that appeared after the body of the chapter had been completed. The second review (74 pages), by Gordon K. Anderson, covers the Organic Chemistry of Gold. This article covers the literature up to mid-1980 and is the first major review of this topic to appear since 1970. Extensive coverage of synthesis and reactivity of Au(1) and Au(II1) compounds containing n and r ligands is presented, together with comparisons of the reactivities of both oxidation states. The chapter concludes with a brief comparison of organogold compounds with those of other metals, particularly Pt and Hg.
Organometallics, Vol. 2, No. 3, 1983 479 Chapter 3 (42 pages) is entitled Arsonium Ylides and represents a useful contribution from Huang Yaozeng and Shen Yanchang of the People’s Republic of China. While this general topic has been reviewed recently elsewhere, this article focuses to some extent on studies emanating from Shanghai. This is indeed a timely review of these results, since the authors point out that “our work was interrupted, and some of our findings were delayed in publication for about 15 years”. Methods of preparation, structure and physical properties, chemical reactivity, and synthetic applications are covered. The fourth contribution (104 pages), by Wolfgang A. Herrmann, covers the rapidly growing number of compounds containing a Methylene Bridge. Comprehensive coverage of synthesis, structure and bonding, spectroscopic characterization, and chemical reactivity of p-methylene compounds is provided, together with discussion of the catalytic relevance of these species to CO reduction on metal surfaces. Concluding sections on group 4A congeners of p-methylene compounds and p-(w,w’)-alkanediyl complexes add perspective and provide a view of some synthetic challenges for the future. An extensive addendum is provided, covering numerous developments in this burgeoning area that were published after the main text was submitted. Nucleophilic Displacement a t Silicon: Recent Developments and Mechanistic Implications (47 pages), by R. J. P. Corriu and C. Guerin, reviews recent progress in this area, with special focus on factors controlling the stereochemistry of substitution and on a frontier orbital approach to understanding the mechanisms of these reactions. In view of the authors’ prominent contributions to this field, it is not surprizing that many of the literature citations are drawn from their own work. The final article, The Biological Methylation of Metals and Metalloids (43 pages), by John S. Thayer and F. E. Brinckman, concentrates on rate studies of transmethylation reactions, both in vitro and in vivo, with additional discussion of the mechanisms of these reactions. Once again, an addendum of up to date literature citations is provided. While the price, and the diversity of topics, make this volume an unlikely acquisition for the individual chemist, it will surely join the ranks of its 19 predecessors on the shelves of every chemistry library. Russell P. Hughes, Dartmouth College
Gmelin Handbook of Inorganic Chemistry, 8th Edition, Sn, Organotin Compounds, Part 9, Triorganotin-Sulfur Compounds. H. Schumann and I. Schumann, volume authors, H. Bitterer, volume editor. Gmelin Institut fiir Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin/Heidelberg/New York. 1982. iv + 276 pages. DM 727, $322.80 (in English). As the authors of this volume state, “Organotin-sulfur compounds are among the most important industrial organometallic compounds”. For this reason, many organotin compounds containing a tin-sulfur bond have been prepared in industrial, as well as in academic laboratories. Of these, many have been either inadequately reported (in patents) or inadequately characterized, having been isolated only as ”pot-bottoms” from their reaction mixtures. Nevertheless, many organotin-sulfur compounds have been characterized, either adequately or to some extent, and, of these, those in which the organotin moiety is a triorganotin group provide grist for the Schumann’s tin mill in the present volume. Only compounds of type R3SnSR’are covered in this book. The substituent R’ can vary widely. It can be an alkyl or aryl group, but it may also be part of a sulfur-functional group such as thiocarbamate, thiocarbonate, isothiocyanate, isothiourea, monoor dithiocarboxylate, iminodithiocarbonate, thiophosphate, etc. Also covered are compounds of type R,SnSH, R3SnS02, R&ISS~R’~, R3SnSGeR’3,R$nSBR’*, R3SnSNa, R3SnSMn(CO)S, and (R3SnSR’)Cr(CO)5and other metal carbonyls in which trialkyltin mercaptide5 are present as ligands. As usual,syntheses and all physical, spectroscopic, and chemical properties are provided in great detail, as is information on applications and biological properties. The comprehensive literature coverage (through the end of 1980) includes journal articles, reviews, patents, theses, and conference reports. The patent coverage is important and is based on those patents abstracted by “Chemical Abstracts”.
480 Organometallics, Vol. 2, No. 3, 1983 The detailed accounts of the currently available review literature which might be useful to the reader are a valuable feature of the organotin series. The general review literature (with "organometallic compounds", "organometallic compounds of the main-group 4 elements", "organotin compounds" as categories) is up-dated and further collections of reviews and patents on organotin chalcogenides and organotin-sulfur compounds are pertinent to the subject matter of this volume. A useful empirical and substituent group formula index concludes the book. Together with the fairly detailed table of contents, this makes it rather easy to find the compounds one is looking for. The Gmelin Handbook volumes are not really suitable for browsing, but as comprehensive reference works, they are invaluable. No chemical library should be without them. Further volumes of the Gmelin organotin series will deal with the remaining organotin-sulfur compounds, including the industrially important R2Sn(SR')2 derivatives. Dietmar Seyferth, Massachusetts Institute of Technology
Gmelin Handbook of Inorganic Chemistry, 8th Edition, Uranium. Supplement Volume A5. Spectra. W. T. Carnall, Hannah M. Crosswhite, Henry M. Crosswhite, D. J. Lam, B. W. Veal, and B. Kanellakopulos, volume authors. C. Keller and K.-C. Buschbeck, volume editors. Gmelin Institut fur Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften and Springer-Verlag, Berlin/Heidelberg/New York. 1982. v + 269 pages. DM 717, $318.40. The Gmelin Institute is presently involved in a major effort to update the 1936 "Uran" volume of the "Handbuch der Anorganische Chemie" series. Part A covers the element uranium, part B, the metal and its alloys, part C, certain of the compounds, part D, the solution chemistry, and part E, the coordination compounds. Thii volume (A5) deals with the spectroscopy of uranium and its compounds (including organometallic compounds). It covers the scientific literature through 1979. In chapter 1, Henry M. Crosswhite (Argonne National Laboratory) provides a comprehensive discussion of the atomic spectra of gaseous uranium atoms and ions (not of great interest to most organometallic chemists). In chapter 2, William T. Carnall (Argonne National Laboratory) presents a succinct and up-to-date
Book Reviews picture of current results and theory concerning the absorption and luminescence spectra of uranium compounds. The comprehensive coverage is by oxidation state, and adequate critical coverage is given to organouranium compounds. Chaper 3, by Hannah M. Crosswhite and William T. Camall (ArgonneNational Laboratory), discussesthe X-ray emission spectrmopy of uranium and will not be useful to most organometallic researchers. Photoemission spectroscopy is the topic of chapter 4 by Boyd W. Veal and Daniel J. Lam (Argonne National Laboratory). Although this chapter presents an excellent discussion of XPS and UPS results for purely inorganic uranium compounds (e.g., oxides, halides, nitrides), there is no discussion of uranium organometallic compounds nor even a reference to direct the reader. This is disappointing since a considerable and important literature of gas-phase UPS studies now exists for organouranium compounds. Fortunately, some discussion of these results is provided in a Supplement Volume E2 chapter by B. Kanellakopulos. Chapter 5 of the present volume by Henry R. Hoekstra (Argonne National Laboratory) summarizes the vibrational spectra of uranium compounds. Unfortunately, the coverage largely focuses upon uranyl compounds, and even important inorganic topics such as UF, and U(BH& are not given full coverage. There is no mention of the numerous studies invovling organometallic compounds nor is the reader referred to the aforementioned chapter by Kanellakopulos that fortunately does touch upon some aspects of the vibrational spectra. Chapters 6 , 7 , and 8 by Basil Kanellakopulos (Kernforschungszentrum Karlsruhe) discuss EPR, NMR, and Mossbauer spectroscopy, respectively. All give excellent expositions of the subject matter, and the former two, although not dealing specifically with organouranium compounds, will be useful to organometallic chemists interested in f elements. Kanellakopulos directs the reader to his chapter in volume E2 as well as to other literature for discussion of the NMR spectra of uranium organometallic compounds. Post-1979 EPR data on organouranium complexes could not be included. As in all Gmelin volumes, volume A5 provides an explanation of the Gmelin classification scheme and a table of conversion factors. This monograph clearly provides a wealth of spectroscopic information on uranium compounds and will be of general interest to actinide researchers. The coverage of uranium organometallic compounds, however, is rather light, and in view of the high price, this volume seems most appropriate for institutional library purchases. Tobin J. Marks, Northwestern University
