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Molecular Chemistry of the Transition Elements. An Introductory Course

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Francois Mathey and Alain Sevin. John Wiley & Sons: Chichester, 1996. ISBN 0 471 95919 7. Paper, $44.95.

This book presents an introduction to the organometallic chemistry of transition metals. It contains a brief history of organometallic chemistry, two chapters on fundamental concepts and main functional groups in organometallic chemistry, and two chapters on applications in organic synthesis and homogeneous catalysis. It is meant for undergraduate students with a strong background in mathematics and physics who are familiar with concepts of atomic orbitals and frontier molecular orbitals as well as symmetry and group theory. The topics covered by the book are logically arranged. First, different ligands and electron counting methods used for coordination complexes are introduced, then theoretical aspects involving molecular orbitals in metal complexes are presented. This approach is used throughout the book. The more descriptive part, such as the review of principal types of reactions in transition metal chemistry, is followed by a more theoretical one, for instance molecular orbital approach to oxidative addition and reductive elimination. The text provides very good descriptions of main functional groups in organometallic chemistry, including metal carbenes and metal–metal bonds, all supported with analysis of molecular orbital diagrams. The last two chapters present applications of transition metal complexes. They include the usage of zirconium, iron, and chromium compounds in organic synthesis and examples of homogeneous catalysis in such processes as hydrogenation, hydroformylation, and polymerization. The appendix gives concise information on group theory and molecular orbitals in selected model complexes. Its section entitled “Structures and Nomenclature in Complexes” presents different diagrams for metal orbitals depending on the symmetry of the metal complex. I find the extensive analysis of molecular orbitals very useful and unique for this book, especially the evolution of

energies of MO when the geometry of ligand arrangement changes. Unfortunately, not all the MO diagrams are clearly related to the text or fully labeled. For instance, the MO diagram for CO shows only 8 electrons, whereas the description in the text talks about 10 electrons. The diagram representing MO correlations during oxidative addition classifies the orbitals as symmetrical and antisymmetrical with respect to the plane—which is so badly defined that the whole point is lost, I am afraid. It would also help to indicate that in this case, these MOs represent ML4 fragments. There are several more inconsistencies that make it difficult to follow the authors’ ideas. For instance, the electron count is incorrect in some cases (e.g., pp 125, 128); the titles of subsections are switched in the part dealing with triple M≡M bonds; the basicity of phosphines is expressed in terms of the pKa of the phosphine; the bonding in boron compounds is more than once referred to as three-electron, threecenter; occasionally the charges or subscripts in formulas are omitted or misplaced (e.g., in two cases on p 124, and on pp 131, 141, and 155); and the last section of the Appendix has a title irrelevant to its content. The above list of errors is not complete. Nevertheless, I find this book very useful as a supplemental reading for undergraduates taking advanced inorganic chemistry or a similar course. It should also be very helpful in planning or choosing the lecture topics for such a course. Each chapter has an ample list of literature references, some as recent as 1996, the year of publication of this book! This is another strong point of this text, in addition to the treatment of MO. The size of the book (only 209 pages, soft cover) makes it user friendly. The brief description of the topics and many pictorial diagrams should stimulate the interest of the student first exposed to this topic. Magdalena Pala Department of Chemistry University of Wisconsin–River Falls River Falls, WI 54022

JChemEd.chem.wisc.edu • Vol. 75 No. 5 May 1998 • Journal of Chemical Education

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