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Books > Science & Mathematics > Chemistry > Inorganic chemistry
The aim of this compilation has been to provide a comprehensive,
non-criti cal source of information concerning organometallic
compounds. The scope is limited to the compounds containing at
least one carbon-metal bond. The in formation includes methods of
preparation, properties, chemical reactions, and applications. The
First Edition comprised the literature from 1937 to 1958. The
Second Edition is completely revised and extended through 1964. The
literature prior to 1937 was thoroughly covered by E. Krause and A.
von Grosse in I~ie Chemie der meta11-organischen Verbindungen, "
Verlag von Gebrueder Borntraeger, Berlin, 1937. Our work consists
of three volumes. Volume I contains derivatives of the transition
metals of Groups III through VIII of the Periodic Table. Volume II
contains derivatives of germanium, tin, and lead. Volume III
contains derivatives of arsenic, antimony, and bismuth. The
compilation is based on searches through Chemical Abstracts. The
col lection of references for 1964 was completed before the Subject
Indexes to Volumes 60 and 61 of the Abstracts were available; thus
some omissions in the coverage of that year are possible. We have
attempted to make the coverage of the literature complete in order
that the compilation may have best utility to the chemist, chemical
engineer, patent attorney, and editor. In the interest of brevity,
certain numerical data are omitted, but references to the original
literature are given. Yield data are rounded to two significant
figures. Wherever possible, tables have been used. The entries in
the Bibliography section include references to Chemical Abstracts.
According to R.H. Crabtree, Metal Dihydrogen and sigma-Bond
Complexes is described as 'the definitive account of
twentieth-century work in the area of sigma complexation'. It
covers not only Kubas' discovery of dihydrogen coordination and the
study of its structure and general properties but also discusses
both the theoretical beliefs and experimental results of bonding
and activation of dihydrogen on metal centers and the coordination
and activation of C-H, B-H, X-H, and X-Y bonds, giving an overview
of 'one of the hottest areas in chemistry'.
In the short time since the first nitroxyl radical was obtained in
1959, a new branch of chemical science has arisen and taken
shape-the chemistry of stable nitroxyl radicals. The present book
was written by E. G. Rozantsev, one of the pioneers in this field
and a prominent specialist on stable radicals at the Division of
Chemical and Biological Processes of the Institute of Chemical
Physics, Academy of Sciences of the USSR. His numerous papers have
contributed greatly to the present situation, wherein nitroxyl
radicals have acquired unusually wide popularity, including the
fields of biology, medicine, chemis try, physics, biophysics, and
instrument construction. A clear illustration of the astonishingly
vigorous development of this new field of chemistry can be given by
the enormous flow of information on the synthesis and use of
nitroxyl radicals. There is no doubt that this monograph, which in
part generalizes the results of many workers studying these
radicals, will be received with interest by specialists working in
this field. The author has not attempted to give an exhaustive
account of the material. His aim is to introduce the reader to this
new field and to show the wide possibilities for using radicals in
scientific experiment. The voluminous bibliography, including many
papers by the author himself which may not be well enough known to
the American reader, will undoubtedly contribute to the usefulness
of the monograph."
Environmental Chemistry is a relatively young science. Interest in
this subject, however, is growing very rapidly and, although no
agreement has been reached as yet about the exact content and
limits of this interdisciplinary subject, there appears to be
increasing interest in seeing environmental topics which are based
on chemistry embodied in this subject. One of the first objectives
of Environ mental Chemistry must be the study of the environment
and of natural chemical processes which occur in the environment. A
major purpose of this series on Environmental Chemistry, therefore,
is to present a reasonably uniform view of various aspects of the
chemistry of the environment and chemical reactions occuring in the
environment. The industrial activities of man have given a new
dimension to Environ mental Chemistry. We have now synthesized and
described over five million chemical compounds and chemical
industry produces about one hundred and fifty million tons of
synthetic chemicals annually. We ship billions of tons of oil per
year and through mining operations and other geophysical
modifications, large quantities of inorganic and organic materials
are released from their natural deposits. Cities and metropolitan
areas of up to 15 million inhabitants produce large quantities
ofwaste in relatively small and confined areas. Much of the
chemical products and was te products of modern society are
released into the environment either during production, storage,
transport, use or ultimate disposal. These released materials
participate in natural cycles and reactions and frequently lead to
interference and disturbance of natural systems."
1.1 The Role of Silicon as a Semiconductor Silicon is unchallenged
as a semiconductor base material in our present electronics indu
stry. The reasons why it qualifies so strongly for this particular
purpose are manyfold. The attractive combination of physical
(electrical) properties of silicon and the unique properties of its
native oxide layer have been the original factors for its
breathtaking evolution in device technology. The majority of
reasons, however, for its present status are correlated with
industrial prosessing in terms of charge units ( economy),
reliability (reproducibility), and flexibility, but also its
availability. The latter point, in particular, plays an important
role in the different long-term projects on the terrestrial
application of solar cells. Practically inexhaustive resources of
silicon dioxide form a sound basis even for the most pretentious
programs on future alternatives to relieve the present situation in
electrical power generation by photovol taics. Assuming a maximum
percentage of 10% to be replaced by the year 2000 would roughly
mean a cumulative annual production of 2 million metric tons of
crude silicon (based on present solar cell standards) ). To
illustrate the orders of magnitude that have to be discussed in
pertinent programs: Today, the industrial silicon capacity of
non-communistic countries (including ferrosili con and other alloys
by their relative Si-content) amounts to some 2 million tons per
year."
Ruthenium Oxidation Complexes explores ruthenium complexes,
particularly those in higher oxidation states, which function as
useful and selective organic oxidation catalysts. Particular
emphasis is placed on those systems which are of industrial
significance. The preparation, properties and applications of the
ruthenium complexes are described, followed by a presentation of
their oxidative properties and summary of the different mechanisms
involved in the organic oxidations (e.g. oxidations of alcohols,
alkenes, arenes and alkynes, alkanes, amines, ethers, phopshines
and miscellaneous substrates). Moreover, future trends and
developments in the area are discussed. This monograph is aimed at
inorganic, organic, industrial and catalysis chemists, especially
those who wish to carry out specific organic oxidations using
catalytic methods.
The present book is based on the work of M.N.Bochkarev,
G.S.Kalinina, L.N. zakharov and S.Ya.Khorshev. The Russian edition
of that book appeared under the same title in 1989 and covered
literature data up to the middle of 1986. Since that time the
number of publications on this subject increased significantly. In
this volume we include all the data published up to the end of
1990, as well as some of the most important relevant articles of
1991. Therefore, this book should be considered as a new book,
devoted to the same problems, rather than as just a translation of
the mentioned issue. This book deals with compounds of scandium,
yttrium, lanthanum and lanthanoids containing direct metal-carbon
bond, Le. with the real organometallic complexes of these metals.
Besides, the volume includes the rare earth complexes, in which
organic ligand is bonded to the metal atom via the atom of another
element of the Periodic Table. In other words, the book includes
all classes of rare earth organoderivatives. Carboxilates,
fl-diketonates and related chelates are the exceptions, because
their properties are closer to inorganic compounds and they were
fully described elsewhere. It should be noted, that "rare earth
elements," "rare earth metals," "lanthanoids" and related terms are
used in this book for indicating scandium, yttrium, lanthanum and
the following 14 elements of the Periodic Table.
The term "carbon-functional organosilicon compound" is used for
organosilicon compounds in which a functional group is bonded to an
organic moiety that is in turn con nected to silicon via a Si-C
bond. Thus, only Si-Cn-Y com pounds (Y designates a functional
group) will be discussed in this book 1 Si-O-Cn-Y compounds will in
general not be considered, although the latter group does include a
large number of natural substances containing silylated hydroxyl
groups. (Because of the differing importance of various Y groups,
the reader will find some deviation from this restriction).
Finally, compounds containing a silyl group as the functional group
are not considered. An overview of the field of organosilicon
chemistry would show that in the last several decades the
commercial synthesis of organosilicon products has increased
substan tially, both in annual production and also in the
increasing variety of compounds produced. This increase in the
number of commercially available carbon-functional monomers and
polymers (silicone polymers) is most remarkable and is occurring
because new applications are continually being found for these
compounds. As might be expected, the number of publications in this
field is also increasing. The important position of silicon in the
periodic table - between carbon, aluminum, and phosphorus - means
that an understanding of the nature of the bonds in organosilicon
compounds is quite important in order to understand the bonding in
these other areas."
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
The second edition of this textbook is identical with its fourth
German edi tion and it thus has the same goals: precise definition
of basic phenomena, a broad survey of the whole field, integrated
representation of chemistry, physics, and technology, and a
balanced treatment of facts and comprehen sion. The book thus
intends to bridge the gap between the often oversimpli fied
introductory textbooks and the highly specialized texts and
monographs that cover only parts of macromolecular science. The
text intends to survey the whole field of macromolecular science.
Its organization results from the following considerations. The
chemical structure of macromolecular compounds should be inde
pendent of the method of synthesis, at least in the ideal case.
Part I is thus concerned with the chemical and physical structure
of polymers. Properties depend on structure. Solution properties
are thus discussed in Part 11, solid state properties in Part Ill.
There are other reasons for dis cussing properties before
synthesis: For example, it is difficult to understand equilibrium
polymerization without knowledge of solution thermodynamics, the
gel effect without knowledge of the glass transition temperature,
etc. Part IV treats the principles of macromolecular syntheses and
reactions."
The chemistry of transition metal carbyne complexes has become a
highly attractive field during the past twenty years. In recent
years its application to aspects of catalysis and metathesis has
gained considerable interest from inorganic as well as organic
chemists. In addition, organic synthesis by means of metal carbon
multiple bond reagents offers the most sophisticated technology
currently available. In consideration of these developments some of
Professor E. O. Fischer's former coworkers and colleagues felt
obliged to orga nize this NATO Advanced Research Workshop on
Transition Metal Carbyne Complexes in the Bavarian Alps. They have
been encouraged by the fact that most of the distinguished
scientists in the field of metal-carbon multiple bond chemistry had
finally agreed to participate and to present stimulating lectures.
The organizers of the workshop are deeply grateful to the
Scientific Affairs Division of the NATO for the generous financial
support of the meeting in Wildbad Kreuth and for the preparation of
this book. They also feel indebted to acknowledge the generous
support from Wacker-Chemie, BASF, Peroxid-Chemie, Hoechst and
Bayer. Finally they thank the staff of the Hanns-Seidel-Stiftung in
Wildbad Kreuth for providing a pleasant and stimu lating atmosphere
during the meeting."
This translation from the original Russian book outlines the
production of a variety of materials by methods of self-propagating
high-temperature synthesis (SHS). The types of materials discussed
include: hard, refractory, corrosion and wear-resistant materials,
as well as other advanced and specialty materials. The authors
address the issue of optimal parameters for SHS reactions occurring
during processes involving a preliminary metallothermic reduction
stage, and they calculate these using thermodynamic approaches. In
order to confirm the effectiveness of this approach, the authors
describe experiments focusing on the synthesis of elemental
crystalline boron, boron carbides and nitrides. Other parts of this
brief include theoretical and experimental results on single-stage
production of hard alloys on the basis of titanium and zirconium
borides, as well as macro kinetics of degassing and compaction of
SHS-products. This brief is suitable for academics, as well as
those working in industrial manufacturing companies producing hard
alloys and composites for making metal-working machinery or
drilling equipment.
This volume documents the proceedings of the Second Symposium on
Metallized Plastics: Fundamental and Applied Aspects held under the
aegis of the Dielectric Science and Technology Division of the
Electrochemical Society in Montreal, Canada, May 7-10, 1990. The
first symposium on this topic was held in Chicago, October 10-12,
1988 and the proceedings of l which have been chronicled in a
hard-bound volume l As pointed out in the Preface to the
proceedings of the first symposium the metallized plastics find
scores of applications ranging from very mundane to very
sophisticated. Even a cursory look at the literature will convince
that this field has sprouted; and there is every reason to believe
that with all the research and development activities taking place,
new and exciting applications of metallized plastics will emerge.
The program for the second symposium was very comprehensive as it
included 46 papers covering many aspects of metallized plastics.
This symposium was a testimonial to the brisk research activity and
keen interest in the topic of metallized plastics. The success of
this symposium reinforced our earlier belief that there was a
definite need to hold symposia on this topic on a regular basis.
Concomitantly, the third symposium in this vein was held in
Phoenix, Arizona, October 13-18, 1991 and the fourth is planned for
May 16-21, 1993 in Honolulu, Hawaii. As regards the present volume,
it contains a total of 35 papers covering a variety of topics
ranging from very fundamental to very applied.
All existing introductory reviews of mineralogy are written accord
ing to the same algorithm, sometimes called the "Dana System of
Mineralogy." Even modern advanced handbooks, which are cer tainly
necessary, include basic data on minerals and are essentially
descriptive. When basic information on the chemistry, structure,
optical and physical properties, distinguished features and para
genesis of 200-400 minerals is presented, then there is practically
no further space available to include new ideas and concepts based
on recent mineral studies. A possible solution to this dilemma
would be to present a book beginning where introductory textbooks
end for those already famil iar with the elementary concepts. Such
a volume would be tailored to specialists in all fields of science
and industry, interested in the most recent results in mineralogy.
This approach may be called Advanced Mineralogy. Here, an attempt
has been made to survey the current possibilities and aims in
mineral mater investigations, including the main characteristics of
all the methods, the most important problems and topics of
mineralogy, and related studies. The individual volumes are
composed of short, condensed chap ters. Each chapter presents in a
complete, albeit condensed, form specific problems, methods,
theories, and directions of investigations, and estimates their
importance and strategic position in science and industry."
In this brief, renowned inorganic chemist Jay Labinger tracks the
development of his field from a forgotten specialism to the
establishment of an independent, intellectually viable discipline.
Inorganic chemistry, with a negation in its very name, was long
regarded as that which was left behind when organic and physical
chemistry emerged as specialist fields in the 19th century. Only by
the middle of the 20th century had it begun to gain its current
stature of equality to that of the other main branches of
chemistry. The author discusses the evidence for this transition,
both quantitative and anecdotal and includes consideration of the
roles of local and personal factors, with particular focus on
Caltech as an illustrative example. This brief is of interest both
to historians of science and inorganic chemists who would like to
find out how their field began.
In the early 1980s capillary liquid chromatography was being
established; it was a period in which only a few research groups
published a relatively small number of papers on the subject. In
terest has since taken off, and a period of intense development, to
which no end is yet in sight, is now upon us. More investiga tors
and instrument-making firms are now entering the field. This
greater interest has resulted in the rapid appearance of two collec
tions [1, 2] and a series of topical reviews [3-6]. However, it
could hardly be said that all the problems in this area have been
formulated, let alone solved. The preparation of very efficient -
open tubular or packed - microbore columns, for example, remains
more an art than a science, while the relation ship between radial
and longitudinal mass transfer, and the effect of transcolumn
velocity profiles on chromatographic efficiency, have been very
poorly studied. Indeed, recent publications on these subjects have
sometimes, far from clarifying matters, only muddied them further.
Many instrument-making firms are trying to unify their equip ment
so that it is suitable for microbore, conventional (analytical),
and preparative liquid chromatography. This approach has not real
ized the full potential of capillary chromatography, and there also
remains room for improving the performance of capillary columns.
1. G. Engelhardt, H. Koller, Stuttgart, FRG: 29Si NMR of Inorganic
Solids 2. H. Pfeifer, Leizpig, FRG: NMR of Solid Surfaces 3. A.
Sebald, Bayreuth, FRG: MAS and CP/MAS NMR of Less Common Spin-1/2
Nuclei 4. C. J{ger, Mainz, FRG: Satellite Transition Spectroscopy
of Quadrupolar Nuclei 5. D. Brinkmann, M. Mali, Z}rich, CH: NMR-NQR
Studies of High-Temperature Superconductors
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.
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