Mossbauer Spectroscopy Applied to Inorganic Chemistry

Mossbauer Spectroscopy Applied to Inorganic Chemistry. Rolfe Herber. Organometallics , 1985, 4 (6), pp 1148–1148. DOI: 10.1021/om00125a900. Publicat...
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1148 Organometallics, Vol. 4, No. 6, 1985 with the formation and application of various allenic alcohols and allenic aldehydes and ketones. Chapters six and seven treat allenic acids and their derivatives and heterosubstituted allenes, respectively. Chapter eight handles various haloallenes. Chapter nine discusses cycloaddition reactions and the last chapter miscellaneous reactions (organometallic allenes and diverse Claisen rearrangements) of allenes. Throughout the monograph there is a near even balance between the modes of preparation and the synthetic uses of the various allenes described. There are over 1000 references to the original literature up through 1982. The authors have done a good job of focussing upon and bringing into the main stream of modem organic chemistry, a functionality with unique properties that, until recently, has been under appreciated. It is written in a lucid style easily followed and appreciated by the specialist and the general organic audience alike. For the specialist it is a handy compilation of the topic in a single monograph and for the wider audience a ready introduction and good source of reference on the subject. Peter J. Stang, The University of Utah Mossbauer Spectroscopy Applied to Inorganic Chemistry. Vol. 1. Edited by G. J. Long. Plenum Press: New York/London. 1984. xviii-667 pages. $92.50 This volume has a great deal to offer the readers of Organometallics, despite the fact that-strictly speaking-only one part of one chapter (out of 18) is specifically devoted to compounds having one or more metal-to-carbon chemical bonds. Nuclear y-ray resonance spectroscopy is among the most thoroughly reviewed and anthologized fields of physical science. Nevertheless, there is much in this volume which provides a fresh viewpoint or a special perspective in an area of inorganic chemistry and solid-state physics and which is deserving of close scrutiny by investigators whose major interest is in organometallic compounds. An introductory chapter by the editor reviews briefly the fundamental ideas underlying Mossbauer spectroscopy, followed by discussions of spectrometers and their calibrations (Cranshaw), data reduction and refinement (Longworth), and Mossbauer isomer shifts (Shenoy). X-ray and conversion electron scattering techniques (Longworth) are developed to provide a useful contrast to the usual transmission experiments. These chapters briefly introduce the individual topics, and their bibliographies provides an entree into the literature which will be useful to the interested reader. The extensive (93 pages) discussion of the electric field gradient and quadrupole interaction (Spiering) provides an indepth treatment of this hyperfine interaction and deals not only 3 / 2 spin transitions in 57Feand l19Sn but with the familiar also with the more complex situations where both the magnitude and sign of Vzz can be evaluated from the data. A detailed

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Book Reviews treatment of sodium nitroprusside is used to illustrate the evaluation of the EFG tensor and the mean square displacement tensor in the presence of the Gol’danskii-Karyagin effect. Magnetic materials are considered in two separate chapters. One (Cranshaw and Longworth) develops the fundamentals of the nuclear Zeeman effect, while a separate chapter (Johnson) is devoted to studies of restricted dimensionality (principally 1D) systems. Relaxation phenomena (Hoy) are considered primarily for the well-studied cases involving S7Fe,with examples taken for the several known spin states of this nuclide in chemical compounds. Two related chapters provide an overview of the coordination chemistry of iron (Reiff and Long) and of spin transitions and crossover phenomena in ferrous complexes (Gutlich), and these review in a readable manner the very large research effort which has gone into these two areas. The dominance of the 67Fe nuclide in Mossbauer studies is further emphasized by the chapters on the application of this spectroscopy to the study of biological systems (Dickson), heterogeneous catalysis (Berry),and silicate minerals (Coey), in which essentially all of the information which is reviewed pertains to the chemistry and physics of iron-containing materials. This point is even more obvious in the very brief overview of archaeologicalmaterials studies (Longworth) in which the use of 67Fereporter atoms is taken for granted. The final two chemical chapters deal with the structure and bonding in tin compounds and of gold-containing materials (both by Parish) and survey the work done with representative “non-iron” Mossbauer active atoms. In terms of the chemistry of organometallic compounds it must be borne in mind that the present offering is but one volume in what is projected as an ongoing enterprise. Thus,one might search here in vain for a discussion of the extensive Mossbauer work on organoiron complexes, of mention of the significance of the Gol’danski-Karyagin effect in organotin structure studies, or the extensive literature on intercalation and mixed-valence compounds which have received a great deal of attention in recent years. Finally, virtually no reference is made to studies using any of the rare-earth (both 4f and Sf) reporter nuclides, of the investigations using lBI, and of noble gas complexes, inter alia, which, in a book bearing the title of the present one would be surprising, were not future additional volumes by the same editor already in the advanced planning stage. Despite these minor criticisms and the not-so-minor price, this book is a welcome survey of an extensive body of information and will be an obligatory addition not only to research libraries but also to the bookshelves of many inorganic and organometallic chemists, especially those who deal with the chemistry of compounds to which the Mossbauer technique can be fruitfully applied. Rolfe H. Herber, Rutgers, The State University