Chemical Education Today
Book & Media Reviews Electron Transfer Reactions: Inorganic, Organometallic, and Biological Applications Advances in Chemistry Series 253. Stephan S. Isied, Ed. American Chemical Society: Washington, DC, 1997. xxii + 439 pp. ISBN 0-8412-3456-6. $170.
This delightful volume contains 24 papers presented at a conference at Stanford University in March 1995, organized to celebrate the 80th birthday of Henry Taube and to commemorate his contributions to inorganic chemistry. The book begins with a short chapter by Taube in which he outlines the historical context of his work on electron transfer reactions and the effects of backbonding on reactivity. Following this, the papers are organized around three themes. Part I examines “Electron Transfer Applications in Organometallic Chemistry”; Part II discusses “Electron Transfer and Mechanistic Inorganic Chemistry”; and Part III considers “Electron Transfer and Transition Metals in Biology”. The wide range of topics and applications exhibited by the six chapters in the first section clearly demonstrate Taube’s tremendous influence on all areas of chemistry. From the use of osmium complexes in organic synthesis (W. D. Harman) to the development of a commercial methane to methanol synthesis (R. A. Periana) to zirconium polymerization catalysts (D. E. Richardson), the importance of the methodology and philosophy of Taube’s research is made apparent. The other three chapters in this section are I. Bytheway, J. S. Craw, G. B. Bacskay, and N. S. Hush, “Structure and Bonding in Molecular Hydrogen Complexes of Osmium(II)”; J. N. Armor and B. H. Toby, “Zeolites Offer Variety as Ligands”; and J. H. Espenson and M. M. Abu-Omar, “Reactions Catalyzed by Methylrhenium Trioxide”. The emphasis in the 11 chapters in Part II is more on basic mechanistic studies, although once again variety prevails. Of particular note is the chapter by I. R. Epstein, K. Kustin, and I. Lengyel, which details Taube’s influence on the design of new oscillating reactions. One section of this chapter makes the case for the participation of chemists in the new discipline of nonlinear dynamics or “chaos” studies and shows the application of nonlinear dynamics in the observation of Turing patterns (spontaneous generation of order in an open homogeneous chemical system) in an oscillating reaction. The other chapters in this section are R. J. Geue, J. V. Hanna, A. Hohn, C. J. Qin, S. F. Ralph, A. M. Sargeson, and A. C. Willis, “Steric Effects in Redox Reactions and Electron Transfer Rates” (cobalt hexaamine systems); C. Creutz, “Intrinsic Barriers to Atom Transfer Between Transition-Metal Centers”; D. M. Stanbury, “Nuclear Factors in Main-Group Electron Transfer Reactions”; D. Graff, J. P. Claude, and T. J. Meyer, “Calculation of Rate Constants from Spectra: Nonradiative Decay and Electron Transfer”; J. F. Endicott, M. W. Perkovic, M. J. Heeg, C. K. Ryu, and D. Thompson, “Ligand-Induced, Stereochemical Relaxation of Electronic Constraints in a Simple Chemical Process: Examples from Hexaam(m)ine Cr(III) Photophysics”; P. C. Ford and W. T. Boese, “TimeResolved Infrared Studies of Migratory Insertion Mechanisms in Manganese Carbonyls”; A. Haim, “Redox Reactions of
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Binuclear Complexes of Ruthenium and Iron: Kinetic vs. Thermodynamic Control and Activation Effects”; I. S. Moreira and D. W. Franco, “Electron Delocalization through the Disulfide Bridge”; M. J. Sisley and R. B. Jordan, “Kinetic and Equilibrium Studies of the Reactions of Cysteine and Penicillamine with Aqueous Iron(III)”; and Z. N. Rocha, G. Chiericato, and E. Tfouni, “Hydrolysis of Coordinated Nitriles and Linkage Isomerization Reactions in Ruthenium Ammine Complexes with Nitriles and Amides”. For the general reader, the last section, which provides biochemical applications, may be the most interesting. E. I. Solomon, M. D. Lowery, J. A. Guckert, and L. B. LaCroix (“Electron Transfer in Bioinorganic Chemistry: Role of Electronic Structure and the Entatic State”) discuss blue copper proteins and the idea that the protein enhances electron transfer by imposing the reduced geometry on the oxidized copper site. S. S. Isied (“Long-Range Intramolecular Electron Transfer Reactions across Simple Organic Bridges, Peptides, and Proteins”) details extensions of basic ET studies to cytochrome c systems. The uses of ruthenium complexes to inhibit DNA synthesis and tumor growth, probe DNA structure, and study long-range ET are discussed in two chapters: M. J. Clarke, “Ruthenium in Biology: DNA Interactions”, and R. E. Shepherd, Y. Chen, S. Zhang, F. Lin, and R. A. Kortes, “Ru(II)-Polyaminopolycarboxylate Complexes for Improved DNA Probes”. J. K. Hurst (“The Role of Inorganic Chemistry in Cellular Mechanisms of Host Resistance to Disease”) looks at the generation of HOCl and the role of hydrogen peroxide as microbicides; and in the last chapter, E. Deutsch (“Applications of Taube Insights to Nuclear Medicine: In Vivo Inorganic Chemistry”) details the development of new heart imaging radiopharmaceuticals. This is a very attractively produced volume. The writing is generally clear and quite uniform and will be accessible to general readers. A number of color plates are also included. All the papers appear to have been updated since the conference. Many of them have references from 1996 and even 1997. Besides providing a most useful collection of papers based on electron transfer, I believe that this volume should have significant pedagogical use, especially in advanced undergraduate courses. In almost every chapter the authors take care to show how the basic work and philosophy of Henry Taube is tied to their work. His emphasis on basic blocking and tackling (kinetic, thermodynamic, isotopic studies) as the cornerstone for advancing chemical knowledge is cited time and again. In the Periana chapter on methane oxidation, for example, a page from Taube’s original notes shows his use of basic information in the design of a new catalyst. Advanced topic or advanced inorganic courses with ET emphasis could use this book as a major reference. Richard G. Scamehorn Ripon College Ripon, WI 54971
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Journal of Chemical Education • Vol. 75 No. 6 June 1998 • JChemEd.chem.wisc.edu
