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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,
"Time-Resolved Infrared Studies of Migratory Insertion
Mechanisms in Manganese Carbonyls"; A. Haim, "Redox
Reactions of 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.
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