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Volume 1: Fundamentals:
Ligands, Complexes, Synthesis, Purification and Structure (A.B.P. Lever)
This multi-authored volume is intended to contain all the necessary background
material for a proper understanding of the information provided in the other
8 volumes. It is written at a level that presumes a good undergraduate level
appreciation of the basics of chemistry and assumes the material that was covered
in the first edition of Comprehensive Coordination Chemistry (CCC) published
in 1987. It therefore emphasizes knowledge gained since this period.
Section I, “Ligands” contains discussion of the synthesis, structures
and properties of a wide range of common ligands. Section II, “ Synthesis
and Purification” addresses the question of how coordination compounds
can be synthesized, purified and characterized. Inter alia, reaction pathways,
solvents, chromatographic and crystal growth methods are discussed. Section
III, “Reactions of Coordinated Ligands”, follows a similar major
chapter in
CCC (1987), treating the reactivity of a group of ligands including molecules
such as NO and CO2, oximes and nitriles. Section IV, “Stereochemistry,
Structure and Crystal Engineering”, deals with lone pair and outer sphere
effects, hydrogen bonding and crystal engineering. Section V, “New synthetic
methods” deals with a wide range of methods of synthesis.
Volume 2: Fundamentals: Physical Methods, Theoretical Analysis and Case Studies (A.B.P. Lever)
Section I, “Physical Methods” is the largest section and covers a plethora of modern techniques from Synchrotron, to X-Ray, to Vibrational and Electronic, to Photoelectron and Mass spectroscopies and to Electrochemistry and Magnetism. Section II, ‘Theoretical Models, Computational methods and Simulation”, another large section deals with the myriad modern theoretical models and computational techniques, while Section II, ‘Software” briefly highlights current computational computer packages. Section III “Case Studies” presents 8 studies of different problems in coordination chemistry illustrating how the various methodologies, techniques etc. can be brought together to provide a clear understanding of the system at hand.
Volume 3: Coordination
Chemistry of the s, p and f Metals (G.F.R. Parkin)
Volume 2 describes the Coordination Chemistry of the s-, p- and f-block Metals.
Chapter 1 is concerned with the 1s and 2s metals and describes trends in the
development of their chemistry since the mid-1980's, such as the increased use
of sterically bulky ligands, recognition of importance of non-ionic interactions,
reappraisal of the 'spectator' role of s-block ions, and the application of
computational methods.
Chapter 2 is concerned with the chemistry of scandium, yttrium and the lanthanides
and is discussed according to the nature of the ligand in which the donor is
from groups 14 to 17. Divalent and tetravalent lanthanide chemistry is also
described.
Chapter 3 describes the chemistry of the actinides, including the historical
development. The chemistry described is subdivided according to whether the
actinide is early (thorium to plutonium) or late (the transplutonium elements).
Within this subdivision, the chemistry is further classified according to the
oxidation state of the metal (ranging from +3 to +7), and the type of donor
(ranging from elements of Group 15 to 17). The use of chelating ligands as extractants
and as biologically relevant ligands is described.
Chapter 4 describes the chemistry of aluminum and gallium. In addition to aluminum(III)
and gallium(III) coordination complexes, this chapter also focuses on complexes
with aluminum-aluminum and gallium-gallium bonds, and also describes cyclogallenes
and metalloaromaticity.
Chapter 5 describes the chemistry of indium and thallium, including subvalent
compounds of In(II), Tl(II) and Tl(I). Applications of indium and thallium complexes
are also described.
Chapter 6 describes the chemistry of arsenic, antimony and bismuth, including
a discussion of the role that these elements play in the environment and biology
and medicine. Applications of these complexes are also discussed.
Chapter 7 describes the chemistry of germanium, tin, and lead according to M(IV)
and M(II) oxidation states. Within this classification, the chemistry is further
subdivided according to ligand type, which ranges from elements of groups 13
to 17.
Volume 4: Transition Metal Groups
3-6 (A.G. Wedd)
Volume 3 details developments in the coordination chemistry of groups 3-6 since
1981. It will dove-tail into the equivalent volume of CCC (1987). However, the
volume structure will change to accommodate the new and spectacular developments,
particularly in cluster systems.
Chapters 3.1-3.8 will concentrate mainly on the chemistry of mononuclear centres: group 3; group 4; group 5; group 6. Chapter 3.9 will cover binuclear metal centres featuring intermetallic bonds and link to Chapters 3.10-3.12, the chemistry of polynuclear clusters, mainly polyoxo and polychalogenido.
Volume 5: Transition Metal Groups
7-8 (E.C. Constable, J.R. Dilworth)
This volume presents a survey of significant developments in the chemistry
of groups 7 and 8 of the transition metals since the publication of the first
Comprehensive Coordination Chemistry volumes in 1982. The material for each
element is organised by oxidation state of the metal and also by the nature
of the ligands involved, with additional sections covering special features
of the coordination chemistry and applications of the complexes.
Manganese, technetium and rhenium
The coverage for manganese and rhenium is from 1982, whereas for technetium
the earlier literature is included, as technetium did not feature in the
previous edition of CCC2. The biological role of manganese has been a significant
driving force for recent studies of its coordination chemistry and this area
is treated in some detail, as are the uses of manganese complexes for selective
oxidations. For technetium much of the literature is closely linked to the
applications of 99m-Tc complexes in diagnostic nuclear medicine and the development
of first and second generation agents is placed in the context of the reported
coordination chemistry. The potential role of radioactive rhenium complexes
for therapy is a comparatively recent theme, and is again placed against
the backdrop of a systematic account of the fundamental coordination chemistry
of the element.
Iron, ruthenium and osmium
The coverage for iron commences in 1984-1985 and aims to provide a broad-based
introduction to important advances in the chemistry of this element over
the past twenty years. The comprehensive coverage of the chemistry of iron
over this period would be impossible and the authors have done an admirable
job in selecting the most important papers in the primary literature and
have made extensive reference to the review literature to give as braod an
overview as possible. Similar constraints apply to the coverage of ruthenium
and osmium in both high and low oxidation states. However, the coverage in
these two chapters gives an excellent overview of the primary literature
since 1982 and leads the reader naturally to the important review literature
for these elements.
It would be invidious to pick any particular area of activity in the chemistry
of these elements for particular attention, but very significant advances have
been made in many aspects of the coordination chemistry of iron, ruthenium
and osmium. Our understanding of the roles which iron can play in biological
systems and the subtle chemical control over iron metabolism has increased
enormously since 1987 and they represent beautiful aspects of applied coordination
chemistry. Much iron coordination chemistry is designed to further understand
biomimetic aspects. In low oxidation state ruthenium chemistry, renewed interest
in photovoltaic cells is generating a resurgence in {Ru(bpy)3} chemistry. In
high oxidation state ruthenium and osmium chemistry, the utilisation of complexes
as increasingly selective catalytic or stoichiometric oxidising agents shows
no sign of abating.
Finally, I should like to thank the authors involved with these three elements
for their fortitude in approaching such a potentially enormous task with good
humour and positive attitude.
The contributors are all internationally acknowledged experts in the areas they have reviewed.
Volume 6: Transition Metals
Groups 9-12 (D.E. Fenton)
This volume is concerned with fundamental developments in the coordination
chemistry of the elements of Groups 9 - 12. The starting point for review
is 1982. The individual chapters cover the coordination chemistry of Cobalt,
Rhodium,
Iridium, Nickel, Palladium, Platinum, Copper, Silver and Gold, Zinc and Cadmium
and Mercury.
The material is selected in such a way to give the most effective review of discoveries and new interpretations. The style of coverage uses formal oxidation state (highest to lowest) and the nature of the ligand donor atom to define progression through these chapters. Uni- up to polydentate ligands (cyclic and acyclic) and mono- through oligo- to polynuclear species are covered with an emphasis on compounds for which full structural characterisation is available. The relevance of the chemistry to bio-inorganic chemistry, materials chemistry, and industrial application as catalysts will be introduced and cross-referenced to fuller discussion of these in Volumes 6 - 9. Comment will also be made on application of complexes in nanotechnology, and the molecular modelling of complexes.
Volume 7: From the Molecular
to the Nanoscale: Synthesis, Structure and Properties (A. Powell, M. Fujita,
C. Creutz)
This volume describes recent progress in synthetic coordination chemistry,
which has led to the production of materials displaying nanoscopic structural
motifs. The availability of increasingly powerful structure determination
methods such as area detection for single crystal X-ray diffraction and
high-energy
electron microscopies has been a key aspect to the development of this area.
It is now possible to determine the structures of very large clusters, aggregates
of metal ions, and coordination polymers to atomic resolution on a routine
basis. In particular, the field of coordination polymers has been explosively
developed thanks to the development of X-ray diffraction methods. Such development
in structural determination is fed back to the precise design of the structures
and properties of coordination materials. For example, unique properties
of coordination polymers (gas absorption, magnetism, etc) have been explored
through
molecular-level designing.
In the first chapter the synthesis and structures of new heteropolyoxoanions and related systems are discussed. Such systems can enclose nanoscopic spaces and can be regarded as “nanoreactors”. Clusters containing fragments of the lattices of semiconducting materials such as CdSe provide a vivid illustration of the transition from molecular based to extended solid properties and show how the properties in the nanoscale region differ from those at each extreme. These are described in the second chapter. A third physical property for which a bounded system in the sub to nanoscale regime can display unusual behaviour is that of “molecular based magnetism” and the synthetic and structural aspects of such open-shell systems are described in the third and fourth chapters on clusters and aggregates with paramagnetic centres.
The following chapters deal with supramolecular chemistry based on coordination chemistry. This area has been rapidly growing during the last decade making possible the facile production of nanoscopic materials by exploiting weak metal-ligand interactions. From structural aspects, infinite systems (e.g., coordination polymers) and finite systems (e.g., metallodendrimers) are discussed in chapters five and six. Then, templating and self-assembly which are two major synthetic strategies of supramolecular coordination compounds are focused upon in chapters seven and eight. Both methods have shown powerful potentials for the construction of well-defined nanoarchitecture with interesting properties.
The production of mesogenic systems is an area, which has seen significant progress in recent years, and the specific case of the inclusion of metal centres into these is discussed in depth in chapter nine. The volume concludes with an overview of recent progress in the area of sol-gel chemistry.
Species in the nanoscale regime (1 –100 nm) exhibit size-sensitive properties and offer the prospect of controllable properties for catalysis, sensors, molecular circuitry, and other applications. With the tremendous current interest and increasing effort in research in the nanoscience area an examination of the nanoscience-related coordination chemistry literature is well timed.
In this volume, the physical properties of coordination-complex-based systems are examined for species ranging from monometallic “traditional” complexes to ligand-stabilized multimetallic assemblies in metal or semiconductor nanoparticles, dendrimers, and other polymer-based assemblies. Properties to be examined include: molecular electron transfer; electron transfer from the molecular to the nanoscale; magnetism from the molecular to the nanoscale.
Volume 8:
Bio-coordination Chemistry (L. Que Jr., W.B. Tolman)
Volume 8 is devoted to the coordination chemistry of metal ions that are involved
in biological processes. Throughout the volume, relevant biochemical issues
are discussed, but the focus will be on the structures, functions, and properties
of the metal centers in the biomolecules and in relevant coordination complexes,
including synthetic compounds designed as active site models. The volume begins
with an overview of the commonly occurring structural motifs in bioinorganic
chemistry. Sections that follow discuss electron transfer, metal binding, transport
and storage, small molecule binding, activation, and/or evolution (O2, N2, H2,
NOx), hydrolytic and bio-organometallic chemistry, metal-radical arrays, and
DNA and RNA as ligands. The following list of articles by separate contributors
within the section on Dioxygen Activation illustrates the specificity and breadth
of coverage in each section: Heme Peroxidases and Catalase (Meunier), Cytochrome
P450 (Nam), Multimetal Oxidases (Karlin), Dicopper Enzymes (Itoh), Nonheme Diiron
Enzymes (Lippard), Nonheme Monoiron Enzymes (Caradonna), Monocopper Oxygenase
Enzymes (Halcrow), and Molybdenum and Tungsten Enzymes (Garner). In general,
reports of relevant structural models and/or functional mimics are included.
Compounds which were prepared with the intention of acting as models/mimics
but which were unsuccessful in this regard are reported in Volumes 3 - 6.
Volume 9:
Applications of Coordination Complexes (M.D. Ward)
This volume is concerned with actual and potential applications
of metal coordination complexes. The two most obvious applications of coordination
complexes are
in catalysis and medicine, and much of the volume covers these two areas
in some detail. Thus, metal complexes in catalysis covers all of the important
areas of homogeneous catalysis by reaction type (hydrogenation, polymerisation,
carbonylation, C-C and C-X cross-couplings, Lewis-acid catalysis, addition
of HX to double bonds, and so on), and also includes developments such as
electrocatalysis,
supported catalysts and combinatorial methods in catalysis. Medical applications
of coordination complexes will include sections on chemotherapy, imaging
and diagnostic agents (radioimmuno- and fluoro-imminoimaging, MRI contrast
agents)
and therapeutic agents (radioimmunotherapy and photodynamic therapy).
In addition, other actual (or potential) applications of coordination complexes
in a variety of other fields will be described. These will include metal complexes
as dyes and optical materials (non-linear optics, display devices, optical
data storage, electrochromic materials), for solar energy harvesting, for hydrometallurgical
extraction, and as MOCVD precursors for new materials. In summary, it is intended
that volume 9 should cover the whole range of current and near-future applications
of coordination complexes in the real world. The volume will accordingly be
highly interdisciplinary and will draw on fundamental material described in
all of the other volumes.