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Edited by K. Morokuma and D. Musaev Computational modeling for homogeneous and enzymatic catalysis a knowledge-base for designing efficient catalysts WileyЦVCH 2008 398 pp

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Book Review
Published online in Wiley Interscience 10 August 2009
( DOI 10.1002/aoc.1541
Book Review
Computational modeling for homogeneous and enzymatic
catalysis: a knowledge-base for designing efficient catalysts
Wiley?VCH, 2008, 398 pp.
price �0.00/�6.00 (hardcover)
ISBN 978-3-527-31843-8
This book is an impressive testament to the maturity that computational, in particular, quantumchemical, methods have reached
over the past ca 15 years. Their efficiency and reliability, combined
with the exponential increase in
computer power, have made it
possible to model complex catalytic reactions in detail, often
taking the real systems fully into
account in the calculations. The
knowledge base mentioned in the
subtitle of the book can be understood to refer to the set of computational tools and techniques
available that are well-tested and ready for use in real applications.
The knowledge base can also be taken to refer to the body of
results derived from theoretical and computational studies on
catalytic systems. The detailed insights into, and understanding
of, the mechanisms and energetics of catalytic reactions provide a
base for the further rational development of improved catalysts.
The collection of articles assembled by Morokuma and his longtime collaborator Musaev, two established names in the area
of quantum-chemical modeling of catalytic reactions, beautifully
documents the state of the art of the field. The book?s scope,
as defined in the title, includes homogeneous and enzymatic
catalysis. However, the emphasis is very clearly on metal-catalyzed
homogeneous processes. Of the 15 chapters, four of which were
authored by the editors and their co-workers, only the first
three deal with enzyme reactions; 11 chapters are devoted to
homogeneous catalysis by (transition) metals; and one extends
the scope into heterogeneous catalysis by considering reactions
at transition-metal oxide surfaces. The authors of the individual
chapters are computational chemists who have contributed
significantly to the respective area. The chapters comprise between
15 and 35 pages and mostly review the respective authors? own
work; some also include material by other researchers.
In particular, the field of transition-metal homogeneous catalysis
is very well covered; topics include N2 activation by Zr complexes,
Pd-catalyzed C?C coupling reactions, alkene polymerization
by early-transition-metal and lanthanide metallocenes, alkene
epoxidation catalyzed by polyoxometalates, alkene metathesis by
Mo and Ru carbene complexes, Pt-catalyzed methane activation,
hydrosilylation by a variety of metal complexes, as well as activation
of X?H bonds of small molecules by transition-metal ions (Mn+ ,
MO+ ) in the gas phase. Enzymatic catalysis is represented
by a study on glutathione peroxidase, where the oxidative
dimerization of glutathione was considered with both peroxides
and peroxynitrate as oxidants; an overview of the chemistry of
tetrapyrrole co-factors, in particular the influence of the axial
ligand; and a discussion of combined electron?proton transfer
processes that play a crucial role in photosystem II (oxidation of
dioxygen to water), cytochrome c oxidase (reduction of O2 to
water), nitric oxide reductase (reduction of NO to N2 O), Ni?Fe
hydrogenase and molybdenum CO dehydrogenase (oxidation of
CO to CO2 ).
In terms of the computational methods used, the quantumchemical method of choice in practically all the studies is densityfunctional theory, owing to its very favorable cost?accuracy
ratio. Correlated wave-function methods like MP2 or CCSD(T)
or multireference methods like CASSCF feature only in a few
special situations. There is more variety with respect to the general
approach and the models used in the calculations: while smaller
systems are simply treated completely at the quantum-mechanics
(QM) level, there are different ways of dealing with larger, especially
enzyme or surface, systems. One may either construct an activesite or cluster model, where the environment is represented by
a few selected neighbors or residues; or one can include the full
system by means of combined QM/MM methods that treat the
environment using a classical molecular-mechanics (MM) force
field. The majority of larger systems discussed in the book are
described by a cluster model; however, there are also examples of
QM/MM studies on both enzyme and transition-metal systems.
Overall, the collection of well-written and carefully produced
articles provides a timely panorama of computational studies of
homogeneous and enzymatic catalysis, with an emphasis on the
former. The only missing facet that one would perhaps have
expected to be covered in such a compilation is organocatalysis,
which is a fast-growing field that has attracted a lot of attention
in recent years. One or two well-selected examples from this
area would have nicely rounded off the scope of the book without
unduly inflating its size. In summary, I recommend this book for any
chemistry research library. It is an excellent entry point for anyone
who would like to get an overview of what can be achieved with
today?s computational methods in enzymatic and homogeneous
catalysis. Computational and experimental researchers alike with
an interest in any of the systems discussed in the book should not
miss the respective chapter.
Hans Martin Senn
University of Glasgow, Glasgow, UK
Appl. Organometal. Chem. 2009 , 23, 481
c 2009 John Wiley & Sons, Ltd.
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