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Edited by Jean-Marie Basset Rinaldo Psaro Dominique Roberto and Renato Ugo Modern surface organometallic chemistry WileyЦVCH 2009 725 pp.

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Book Review
Published online in Wiley Interscience: 5 January 2010
(www.interscience.com) DOI 10.1002/aoc.1606
Book Review
EDITED By JEAN-MARIE BASSET, RINALDO PSARO,
DOMINIQUE ROBERTO and RENATO UGO
Modern surface organometallic chemistry
Wiley–VCH, 2009, 725 pp.
price ¤234.00/£ 195.00 (hardback)
ISBN 978-3-527-31972-5
Modern surface organometallic
chemistry is a magnificent 16chapter volume from the Wiley–VCH collection produced in
Weinheim. This book addresses
the major problem of heterogeneous catalysis in industry that
is crucial in terms of feedstock,
energy and environment for our
future. The editors’ approach is elegant and original, because it is
molecular and no longer macroscopic as traditionally in heterogeneous catalysis. The book really is timely, given the spectacular and
successful developments of alkene, alkyne and alkane metathesis,
olefin polymerization and oxidation reactions on surface single
sites in particular in the Basset group (see for instance Basset’s
most recent Accounts of Chemical Research article in 2010) and
other catalytic reactions in other research groups.
Major drawbacks of heterogeneous catalysis are the lack of
selectivity, the requirement of high temperatures, the too short
lifetimes of the catalysts and the difficult or impossible catalyst
regeneration. It is the goal of the editors and authors of this book
to show how it is possible to efficiently overcome these problems
by a molecular control of the catalytically active sites upon rational
design from the atomic level to the nano level. This revolutionary
strategy is now producing a new generation of heterogeneous
catalysts that are much more selective and operate under rather
mild conditions, avoiding the main drawbacks of traditional
heterogeneous catalysts. Very helpful modern physical tools of
surface science and single-site characterization such as in situ IR,
1 H-, 13 C- and 2D-NMR, EXAFS and surface microanalysis as well
as molecular modeling are also discussed in detail in the various
chapters. All the types of surfaces are considered, including those
of oxides (the most commonly used), metal nanoparticles, various
forms of carbon, carbides, nitrides and main-group metals.
The book is divided into two parts, the first part dealing with
the fundamentals, such as the characterization techniques, metal
cluster analogies, molecular modeling and emergence of solid
support, whereas the second one focuses on the applications in
catalysis, organometallic synthesis and hybrid materials.
After a preface by the editors, a timely introductory chapter by
the renowned pioneers Jean-Marie Basset from Lyon and Kaust
and Renato Ugo from Milano indicates the basic concepts of the
molecular approach of surface catalysis. Two beautifully illustrated
chapters follow by the whole Basset group (21 authors each). The
first one is devoted to the preparation of single-site catalysts on
oxides bound to a variety of elements and on metal nanoparticles
prepared via surface organometallic chemistry, and the other to
their catalytic properties. Here is the heart of the book, including
the most imaginative ideas and achievements. Chapter 4, by Crag
Barnes from the University of Knoxville, Tennessee, summarizes
the various known building blocks of nanostructured, singlesite heterogeneous catalysts, including metal-organic frameworks
(MOFs), covalent organic frameworks (COFs), zeolithic imidazolate
frameworks (ZIFs) and spherosilicates. In the 70-page long Chapter
5, the excellent Sidney group of Antony Ward, Anthony Masters
and Thomas Mashmeyer offers a broad view of transition-metal
single-site catalysts from homogeneous to immobilized systems.
These include covalent anchoring, mono-, bis- and tris-silyloxy
organometalics, anchoring of organometallics via the metal center
or on silica or other materials, electrostatic anchoring or adsorption, and encapsulation in zeolithes by templating or using sol–gel.
The merit of this chapter is to carefully analyze and critically compare these different methods. Chapter 6 was co-authored by the
late Osmar Alberto Ferretti, deceased in 2006, and Monica Laura
Casella (who completed the review alone) from La Plata, Argentina.
It is devoted to the controlled preparation of heterogeneous catalysts for chemo- and enantioselective hydrogenation reactions.
This chapter emphasizes the use of heterobimetallic catalysts, prepared by the surface organometallic chemistry approach, whereby
bimetallic interactions are favored. The heterogeneous chiral catalysts prepared are shown to be of very good quality in terms
of chemo- and enantioselectivity, stability and reuse capability.
A short Chapter 7 follows by the well-known Poznan group
of Bogdan Marcinec, Marek Potrzebowski, Ireneusz Kownacki
and Karol Szubert on surface rhodium silyloxide complexes and
their application to catalysis, detailing molecular vs immobilized
transition-metal–silyloxide complexes in catalysis including welldefined rhodium complexes, their solid-state NMR analysis and
mechanistic discussion of hydrosilylation reactions herewith. Narcis Homs and Pilar Ramierez de la Piscina, two former students from
the Basset group now in Barcelona, have authored Chapter 8 on
carbonyl compounds as metallic precursors of tailored supported
catalysts, with a review of all the late transition metals including
supported heterobimetallic carbonyls serving as models to study
the promoter effect of a second metal in heterogeneous catalysis.
In Chapter 9, the Toulouse group of Philippe Kalk, Emmanuel
Lamouroux and Philippe Serp offers an original review on how to
exploit surface chemistry to prepare catalysts by organometallic
chemical vapor deposition (OMCVD), a fine technique involving the deposition of highly dispersed metallic particles onto an
oxide surface. Chapter 10 on the advanced design of catalyst
surfaces with metal complexes for selective catalysis is authored
428
Appl. Organometal. Chem. 2010, 24, 428–429
c 2010 John Wiley & Sons, Ltd.
Copyright Book Review
by Mizuki Tada from Okazaki and Yasuhiro Iwasawa from Tokyo.
It focuses on oxide surfaces for stilbene oxidation, asymmetric
BINOL synthesis, selective alkene hydrogenation and oxidation of
benzene to phenol. Surface organometallic chemistry of d0 metal
complexes, spread in particular in Basset’s laboratory, is the welcome subject again of Chapter 12 by Regina Buffon and Roberto
Rinaldi from the university of Campinas, Brazil. The very interesting
Chapter 12 by Erwan Le Roux from Bergen, Norway, and Reiner
Anwander from Tübingen, Germany, treats the surface organolanthanide and -actinide chemistry. After discussing the structure
and surface properties and grafting strategies, the authors detail
the immobilization of various families of the f-block complexes,
then various catalytic reactions – olefin and methylmethacrylate
polymerization, ring opening polymerization of oxygenated heterocycles – and fine chemical synthesis – alkane activation, olefin
hydrogenation, hydrosilylation, alkyne dimerization, nitroaldol
reaction, hetero-Diels–Alder reaction, Tishchenko reaction and
Meerwein–Ponndorf–Verley reduction. It is pleasing to discover
that Chapter 13 is authored by a mythic name of inorganic and
organometallic chemistry, Robert J. Angelici, from Ames, Iowa,
who is a former Fred Basolo student. Angelici has now produced,
together with Mihaela Lazar, an authoritative and very useful chapter on isocyanide binding modes on metal surfaces and in metal
complexes. Organic isocyanides (or isonitriles) are indeed stronger
σ donors and weaker π acceptors than their pseudo-isoelectronic
cousin CO, and display a rich variety of coordination modes on
transition metals that is elegantly illustrated here. Elsje Alessandra
Quadrelli, a brilliant and very promising young scientist in the Basset laboratory at Lyon, is the single author of the 40-page Chapter
14 on the molecular insight for silica-supported organometallic
chemistry through transition metal silsesquioxanes. These ligands
are excellent molecular models of silica surfaces and as such have
been largely studied, which leads to much improved strategies
towards optimized designs of single-site surface catalysts. As expected, the chapter is beautifully arranged and richly illustrated,
providing insightful information spanning over all the transition
series and over some lanthanides. Chapter 15 by Masaru Ichikawa
and Atsushi Fukuoka from Sapporo deals with surface-mediated
nanoscale fabrication of metal particles and wires using mesoporous silica templates and their shape/size dependency in catalysis. This chapter is rather technical and overlooks key references
of nanoparticles in catalysis. In addition, in the section devoted to
Au nanoparticles (AuNPs) on silica, the masterwork by Haruta that
revolutionized CO oxidation by discovering the requirement of the
small AuNP size (<5 nm) on oxide surfaces, is not even mentioned.
The ultimate Chapter 16 by Elena Cariati, Claudia Dragonetti, Elena
Lucenti, Dominique Roberto and Renato Ugo, i.e. the Milan group
of the co-editors, is devoted to surface-mediated organometallic
synthesis. It deals with oxide surfaces used as solvent-like media for
the syntheses of a large variety of transition-metal carbonyl clusters
with nuclearities up to 18 (with Pt), and also including some heterobimetallic examples. This useful chapter is welcome and well
organized and could even be summarized in modern textbooks.
In sum, the book is of high quality, edited by world leaders in the
area, and written by qualified and well-recognized specialists. It
offers an insightful and innovative look at heterogeneous catalysis
from the point of view of molecular control. It is a ‘must’ not only
for university and chemistry departments, but also for industrial
and academic chemists interested in catalysis; last but not least, it
is also an extremely useful tool for teaching purposes.
Didier Astruc
Université 1 Bordeaux, France
429
Appl. Organometal. Chem. 2010, 24, 428–429
c 2010 John Wiley & Sons, Ltd.
Copyright www.interscience.wiley.com/journal/aoc
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ugo, renate, psaro, dominique, rinaldo, surface, modern, roberts, marie, jean, bassett, 725, chemistry, organometallic, 2009, wileyцvch, edited
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