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Books > Science & Mathematics > Chemistry > Inorganic chemistry
General The making and breaking of carbon-metal bonds is
fundamental to all the p- cesses of organometallic chemistry and
moreover plays a significant role in - mogeneous as well as
heterogeneous catalysis. This rather blunt statement - phasises the
extent to which a proper understanding of the structure, energetics
and reactivity of C-M bonds is at the core of the discipline. In
order to accept it, a proper definition of the terms involved is
required. Quite simply we define the metal-carbon bond in its
broadest sense to embrace carbon linked to transiti- metals,
lanthanides and actinides, and main group metals. We do not dist-
guish between formally covalent single or multiple bonding on the
one hand and q-bonding on the other. In the studies to be described
in the following chapters, the emphasis will be on transition metal
complexes and insofar as the fun- mentals come under scrutiny,
simple metal alkyls or related species (metal al- nyl, alkynyl,
aryl, or allyl) will play an emphatic part. The central role of
metal alkyls and their congeners and especially the role of their
metal carbon linkage in homogeneous catalysis may be appreciated by
considering some key reaction steps leading to their formation or
breakdown. There follows a few prominent examples of transition
metal mediated stoichiometric or catalytic processes: - In
homogeneous hydrogenation of double bonds, the stepwise reaction of
an q2-coordinated alkene with dihydrogen gives first an alkyl metal
hydride, and then the decoordinated alkane by elimination.
Organolithium chemistry occupies a central position in the
selective construction of C-C bonds in both simple and complex
molecules. Paralleling the surge of interest in methods for
asymmetric synthesis, the use of organolithiums in enantioselective
synthesis has witnessed spectacular advances in a little over a
decade. This volume is the first dedicated to a comprehensive
coverage of this important area. It is designed to provide graduate
students and researchers with a rich source of essential
information on synthesising molecules in an enantioselective manner
using organolithiums, and be an inspiration for future
developments. Following an overview chapter summarising the key
milestones, successive chapters, each written by leading experts in
their field, critically survey all the major areas of progress.
1. R.G. Pearson Chemical Hardness - An Historical Introduction 2.
P.K. Chattaraj Density Functional Theory of Chemical Hardness 3.
J.L. Gazqu z Hardness and Softness in Density Functional Theory 4.
L. Komorowski Hardness Indices for Free and Bonded Atoms 5. N.H.
March The Ground-State Energy of Atomic and Molecular Ions and Its
Variation with the Number of Elections 6. K. Sen Isoelectronic
Changes in energy, Electronegativity, and Hardness in Atoms via the
Calculations of 7. P. Politzer, J.S. Murray, M.E. Grice Charge
Capacities and Shell Structures of Atoms 8. R. F. Nalewajski The
Hardness Based Molecular Charge Sensitivities and Their Use in the
Theory of Chemical Reactivity 9. B.G. Baekelandt, R. A.
Schoonheydt, W.J. Mortier The EEM Approach to Chemical Hardness in
Molecules and Solids: Fundamentals and Applications 10. J.A.
Alonso, L. C. Balbas Hardness of Metallic Clusters
It is 25 years since the seminal papers describing the
relationships between the skeletal geometrics and closed shell
electronic requirements of metal clusters were originally
published. The electron counting rules which developed from these
papers, are now to be found in all undergraduate inorganic
textbooks. This volume provides a contemporary account of recent
applications of the methodology and the mathematical foundations of
the rules. In addition it describes how it is possible to
accomondate acception to the rules within a wider framework. The
authors are the foremost authorities in the field and give a broad
introduction to the area.
The French chemist Marcelin Berthelot put forward a classical and
by now an often cited sentence revealing the quintessence of the
chemical science: "La Chimie cree son objet." This is certainly
true because the largest number of molecular compounds were and are
continuously synthesized by chemists themselves. However, modern
computational quantum chemistry has reached a state of maturity
that one can safely say: "La Chimie Theorique cree son objet" as
well. Indeed, modern theoretical chemistry is able today to provide
reliable results on elusive systems such as short living species,
reactive intermediates and molecules which will perhaps never be
synthesized because of one or another type of instability. It is
capable of yielding precious information on the nature of the
transition states, reaction paths etc. Additionally, computational
chemistry gives some details of the electronic and geometric
structure of molecules which remain hidden in experimental
examinations. Hence, it follows that powerful numerical techniques
have substantially enlarged the domain of classical chemistry. On
the other hand, interpretive quantum chemistry has provided a
conceptual framework which enabled rationalization and
understanding of the precise data offered either by experiment or
theory. It is modelling which gives a penetrating insight into the
chemical phenomena and provides order in raw experimental results
which would otherwise represent just a large catalogue of unrelated
facts.
Self-assembly is undoubtedly a topic of special interest in current
chemistry and is related to very wide scientific areas. Recent
progress in this field seems to be featured by the construction of
well-defined discrete systems exploiting complementary hydrogen
bonding as well as coordination bonding. Seven leading
international experts introduce the current topics in this very
interesting field, focusing on two major subjects: organic
assemblies and inorganic assemblies. All researchers who are
interested in molecular recognition, material science,
nanotechnology, and supramolecular chemistry will welcome this book
as an inspiring source for creative research ideas.
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