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Palladacycles .Edited by Jairton Dupont and Michel Pfeffer

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Nucleic Acid–
Metal Ion
Nucleic Acid–Metal Ion
Edited by Nicholas V. Hud.
Royal Society of Chemistry,
Cambridge 2008. 448 pp.,
hardcover £ 89.95.—ISBN
This is an interesting and topical
new book in the RSC Biomolecular
Sciences series. The book is a multiauthored effort with ten individual and
discrete chapters presented from nine different teams. The prime focus of the book is on the
interactions of DNA and RNA and their components with discrete individual metal ions: either
naked metal ions or their aqua complexes. Understanding in this area has increased significantly in
recent years, particularly because of the quantity of
information available from X-ray crystallographic
studies and advances in the level of resolution, and
therefore this book is timely.
The book derives maximum benefit from its
multi-author nature: the contributing teams are
well respected and each individual chapter is
knowledgeable and informative, as well as being
well written and well presented. The selection and
ordering of the topics that make up the ten chapters
contributes to a nice concerted picture, although
perhaps without a strong and continuous thread or
message running through all the chapters, such as
might be found in a single-author book. Given the
focus on naked metal ions or their aqua complexes,
there is a strong representation of RNA-based
chapters in the book, covering the basics of metal
ion binding as well as associated folding and/or
catalysis. However, this is balanced by DNAoriented chapters, which cover the basic binding
modes, coordination of metals to the component
DNA bases (an excellent chapter by Lippert), and
stabilization of quadruplex structures by metal
cations. It is only in DeRoses contribution on
techniques used to study metal–nucleic acid interactions and in Schurrs chapter on theoretical
modeling that attempts are made to take a holistic
view of both the DNA and RNA fields. This is one
slight disappointment, but that is tempered by the
otherwise very high quality of the individual
The final chapter of the book, by Pizarro and
Sadler, is something of a departure from the focus
of the rest of the book. It is a thoughtful, scholarly,
and articulate survey of how more sophisticated
“designed” metal complexes interact with nucleic
acid structures and can find applications in medicine. Since platinum drugs act by binding to DNA
and are used in treating more than half of all cancer
patients who receive chemotherapy, this is an
important topic. However, this chapter goes far
beyond cisplatin, by describing a variety of different DNA-recognition designs and metallodrug
designs that are currently being explored and by
explaining where the activity is or is not related to
the DNA interactions.
The value of this book lies in the way that it
pulls together in one place the current understanding of how naked metals and their aqua complexes
bind to DNA and RNA. In achieving that, it carves
a particular niche, when compared to the various
other books on nucleic acid recognition that are
available, and certainly researchers interested in
the interactions of naked metal or aqua-complexed
metal ions with DNA or (and perhaps more
commonly) RNA will want to have a copy of this
book on their shelves.
Michael J. Hannon
School of Chemistry
University of Birmingham (UK)
This book provides information about the synthesis,
characterization, and applications
of various cyclopalladated complexes. It consists of 15 chapters. Chapter 1 is an introduction by MoralesMorales, containing a definition and classification of palladacycles. A palladacycle is
defined as “any palladium compound containing
one palladium–carbon bond intramolecularly stabilized by one or two neutral donor atoms”. This is
an important class of compounds which is of major
significance in catalysis as well as in materials
science and biological chemistry.
Unfortunately, palladacycles corresponding to
the stricter organometallic definition—“a cyclic
compound with at least one carbon atom replaced
by a metal”—are not considered sufficiently
throughout the book. These species are becoming
more and more important in the catalysis of organic
reactions and deserve appropriate treatment.
Chapter 2, by Albrecht, covers C H bond
activation for the synthesis of palladacycles,
although it is limited to the heteroatom-assisted
case. It is complemented in the third chapter, by
Urriolabeitia, which deals with oxidative addition
and transmetalation as tools for the synthesis of
metallacycles, and in the fourth chapter, by Meneghetti, where other synthetic methods, involving
the in situ formation of the ligand, are considered.
Chapter 5, by Vila and Pereira, deals with simple
transformations of cyclometalated compounds containing donor atoms.
Catalytic aspects are examined in Chapter 8, by
Njera and Alonso, for Heck and Sonogashira
2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2009, 48, 2636 – 2637
reactions, and in Chapter 9, by Bedford, for the
Suzuki reaction, Buchwald–Hartwig amination,
and related reactions. Such types of palladiumcatalyzed reactions have been treated extensively
in other reviews, and these chapters essentially
refer to the use of cyclopalladated structures.
However, these have been shown in most cases to
give rise to palladium nanoparticles, and thus the
complexes might merely act as precursors of the
actual active species. This casts some doubt on the
real importance of cyclometalated structures in
such reactions.
The use of palladacycles as active species in
synthesis is nicely dealt with in Chapters 6 and 10
by Spencer. However, it is not clear why the
majority of catalytic syntheses, which involve C–C
palladacycles, are not covered, despite the fact that
these species are stated in Chapter 3 to be relevant
in palladium(II) chemistry.
Chapter 7, by Djukic, contains a lot of information that is not readily available in the literature,
concerning cyclopalladated compounds as resolving agents for racemic mixtures of ligands.
Other useful information on the use of cyclopalladated compounds for specific purposes is
contained in the following chapters. Chapter 11,
by Donnio and Bruce, deals with a very interesting
topic: ortho-palladated complexes as liquid crystals.
Angew. Chem. Int. Ed. 2009, 48, 2636 – 2637
It provides a detailed description of this relatively
new field. The photophysical properties of these
complexes are nicely described by Neve in Chapter
12. Chapter 13, by Ryabov, addresses another hot
subject, that of the biological aspects of cyclopalladated complexes and anticancer drugs.
Chapter 14, by Gladysz, deals with a quite
specific subject, the increased solubility of cyclopalladated complexes that contain fluorinated
chains. Also in this case, however, the fluorous
cyclopalladated complexes have been shown to be
precursors of palladium nanoparticles in the Heck
and Suzuki reactions.
The last chapter, by Pijnenburg, Korstanje, van
Koten, and Klein Gebbink, gives a detailed outlook
on palladacycles as dendrimers, a rapidly expanding field.
In conclusion, although general aspects have
already been covered in other reviews, the book is
worth reading as it contains a lot of useful
information on specific topics that is not easily
accessible elsewhere.
Marta Catellani
Dipartimento di Chimica Organica e Industriale
Universit degli Studi di Parma (Italy)
DOI: 10.1002/anie.200900610
2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Edited by Jairton Dupont
and Michel Pfeffer. WileyVCH, Weinheim 2008.
417 pp., hardcover
E 139.00.—ISBN 9783527317813
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jairton, edited, michel, palladacycle, pfeffer, dupont
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