Gmelin Handbook of Inorganic and Organometallic Chemistry - 8th edition – serie
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Inbunden, Tyska, 1976
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Inbunden, Engelska, 1984
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Inbunden, Engelska, 1985
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The present volume Uranium C5 covers the physical properties of U0 - the production 2 and preparation of U0 were already treated in Uranium C4, whereas the chemical proper 2 ties will be the subject of the forthcoming part C6. U0 is the most important chemical compound in all aspects of nuclear technology. 2 It is and will be for the foreseeable future the fuel for all light and heavy water reactors as well as (in the mixed crystal with Pu0 ) for the fast breeder reactors. Therefore, the 2 nuclear engineer has to understand the behavior of U0 under all conditions existing during 2 operational (and possibly failure) states of a nuclear reactor, e. g. , not only in the solid state but also to some extent in the liquid and gaseous states. Besides high scientific interest in the sometimes unique or unusual properties, e. g. , at low temperatures, a lot of data and physical properties which are critical for its use as a nuclear fuel have been determined more or less accurately. Creep, swelling, irradiation densification, and fission gas behavior in the fuel are properties which have been evaluated up to the high temperatu res (near the melting point) which may exist in U0 fuel due to its low thermal conductivity. 2 Besides these more technical data there have been accumulated a lot of important physical data, e. g.
Inbunden, Engelska, 1993
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The crystaLLographer usuaLLy needs, as a compLement to his experimentaL work, a smaLL structure data compiLation. My first, some 25 years ago, was a hand-written List of structure types containing space group, unit ceLL data and positionaL atom coordinates. Some 20 years ago, when computers had become a more easiLy accessibLe tooL, a smaLL computer test fiLe was created with the help of Dr. Jan Portheine, which was LabeLLed TYPIX. Assisted by Dr. KLaus Yvon I inserted in the fiLe the somewhat more than 200 inorganic crystaL structure types which were of interest for our research or with which I was famiLiar from my previous experimentaL crystaL structure studies on intermetalLics and tetrahedraL structure compounds. We soon stopped our work on TYPIX because we reaLized that simpLy storing structure data copied from the Literature did not serve our finaL objective. I had, for exampLe, Listed the structures of certain isotypic compounds as separate distinct structure types because, due to a different setting or description given in the originaL Literature, I missed their isotypism.In other cases, with good Luck, I found the isotypism and succeeded in correctLy transforming one description to the other but then did not know which of the different but equivaLent descriptions I shouLd retain in my data coLLection.
Inbunden, Engelska, 1993
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TYPIX is a critical compilation of crystallographic data prepared by E. Parthé at the University of Geneva. It contains over 3200 compounds representative of the structure types found among inorganic compounds. This work contains condensed crystal chemical information about individual structure types as well as an extensive chapter on the crystal chemistry of particular structure families. The aim of the compilation is to clarify and classify published data for intermetallic and other inorganic structures (types found exclusively with halides or oxides are only included for a few special cases). It provides a tool for additional crystal chemical studies and the development of new materials.
Inbunden, Engelska, 1994
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TYPIX is a critical compilation of crystallographic data prepared by E. Parthé at the University of Geneva. It contains over 3200 compounds representative of the structure types found among inorganic compounds. This work contains condensed crystal chemical information about individual structure types as well as an extensive chapter on the crystal chemistry of particular structure families. The aim of the compilation is to clarify and classify published data for intermetallic and other inorganic structures (types found exclusively with halides or oxides are only included for a few special cases). It provides a tool for additional crystal chemical studies and the development of new materials.
Häftad, Engelska, 2013
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The extraordinary quantity of material included in the Gmelin Handbook of Inorganic Chemistry can make it extremely difficult to find a specific compound using only a general un derstanding of the basic rules for the arrangement of the subject matter (the so-called "System ofthe Last Position"). Consequently, subject indexes have been provided for the past few years to individual Handbook volumes, covering only a single section, or in some cases, a complete system number. During this period a comprehensive subject index-the Gmelin Index-was being prepared, whose first volume is now available. The broad distribution and extensive utilization enjoyed by the Gmelin Handbook in Eng lish-speaking countries has led to a decision to publish the Gmelin Index in the English lan guage. This decision was partly based on the fact that since the English language today oc cupies a preeminent position in the field of chemistry, a German-speaking user could utilize an English text much more readily than would be the case for an English-speaking user and a German text.
Häftad, Engelska, 2013
8 024 kr
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The crystaLLographer usuaLLy needs, as a compLement to his experimentaL work, a smaLL structure data compiLation. My first, some 25 years ago, was a hand-written List of structure types containing space group, unit ceLL data and positionaL atom coordinates. Some 20 years ago, when computers had become a more easiLy accessibLe tooL, a smaLL computer test fiLe was created with the help of Dr. Jan Portheine, which was LabeLLed TYPIX. Assisted by Dr. KLaus Yvon I inserted in the fiLe the somewhat more than 200 inorganic crystaL structure types which were of interest for our research or with which I was famiLiar from my previous experimentaL crystaL structure studies on intermetalLics and tetrahedraL structure compounds. We soon stopped our work on TYPIX because we reaLized that simpLy storing structure data copied from the Literature did not serve our finaL objective. I had, for exampLe, Listed the structures of certain isotypic compounds as separate distinct structure types because, due to a different setting or description given in the originaL Literature, I missed their isotypism.In other cases, with good Luck, I found the isotypism and succeeded in correctLy transforming one description to the other but then did not know which of the different but equivaLent descriptions I shouLd retain in my data coLLection.
Häftad, Engelska, 2013
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The GmeLin FormuLa Index published between 1975 and 1980 covered aLL voLumes of the Eighth Edition of the GmeLin Handbook that had appeared up to the end of 1974 in the case of Main VoLumes and up to the end of 1973 in the case of SuppLement VoLumes. The GmeLin FormuLa Index, First SuppLement, continues from there and covers the handbook voLumes published up to the end of 1979. This First SuppLement wiLL consist of eight voLumes, which wiLL appear at intervaLs of four to six months. The basic structure of the FormuLa Index has been fully retained in the First Supplement: The index Lists aLL eLements, compounds, ions, and systems having definite composition that are described in the handbook text. The first coLumn gives the empiricaL formuLa, whiLe the second gives the conventionaL formuLa. The third coLumn Lists the pertinent pages. (The detaiLs are avaiLabLe in "Instructions for the FormuLa Index", on the next pages. ) This First SuppLement was prepared and printed with extensive use of computers. In the future this wiLL allow publication of cumuLative indexes.The procedures were worked out together with the TechnicaL Section of the Gesellschaft fUr Information und Dokumentation mbH (GID), Frankfurt, and I take this occasion to thank them for their generous help. I wouLd aLso Like to thank our printers, Universitatsdruckerei H. SWrtz AG, WOrzburg, for their advice and cooperation.
Häftad, Engelska, 2013
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Alloys of Uranium with Alkali Metals, Alkaline Earths, and Elements of Main Groups III and IV. The description of uranium and its compounds, for which the Gmelin Institute has started a series of volumes supplementing the main volume of 1936, follows in its arrangement closely the order chosen for the transuranium volumes. Part A treats "The Element", Part B "The Metal and its Alloys", Part C "The Compounds", Part D "The Chemistry in Solution", and finally Part E "The Coordination Compounds". Part E, "The Coordination Compounds" comprises two volumes which already have been finished and are available - completely written in English. Series A comprises 7 volumes which are all available. Series C will comprise 14 volumes of which only volume 6 is missing. Series D consists of 4 volumes dealing with the chemistry in solution, which already have been finished and are available. The present volume describes the alloys and the intermetallic compounds with the metals of main groups I to IV - those systems with semimetals such as boron and germanium are to be found in corresponding volumes in Uranium C series. In the volume B 2 main emphasis is given to the binary systems. The most frequently investigated systems are uranium-beryllium and uranium-aluminium because of their special scientific (U-Be) and technological (U-Al) importance.
Häftad, Engelska, 2013
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Häftad, Engelska, 2013
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Astatine is - besides radon and francium - the only natural radioelement which only has short-Lived isotopes, thereby excluding experiments with . . weighable" amounts of the element. This implies that all available data on physics and chemistry of this element are 12 16 based on experiments on the tracer scale with 10- to 10- g - and this will also not change in future because no longer-Lived isotopes as yet known are to be expected. Due to the fact that the only isotope of At occurring in the natural decay series, 219At, results from the 0. 005% a-branching of 223Fr which itself is produced by the only 1. 38% a-branching of 227 Ac - a member of the 235U series - there is no chance to recover substantial amounts of 219At from natural sources for sCientific research of At. All studies, therefore, are being done with the isotopes 209At to 211At having half-lives in the few hours region and being obtained by irradiation of bismuth with a-particles via (a,xn) reactions or by proton irradiation of heavy elements via spallation reactions. The mostly used isotope is 7. 22 h 211At. The fast separation of the obtained At isotopes is no very difficult procedure and is either being done by wet adsorption-precipitation techniques or making use of its high volatility by destilling in air.
Häftad, Engelska, 2013
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The present volume describes organoberyllium compounds containing at least one berylli um-carbon bond, except the beryllium carbides and cyanides. It covers the literature com pletely to the end of 1986 and includes most of the references up to mid-1987. This Gmelin volume is different from all other volumes of the series on organometallic compounds in that it is dedicated to an area of research which has virtually come to a complete standstill. Organoberyllium chemistry has never been a very popular field, and only few workers have contributed to its slow growth, as is seen by the relatively small number of publications in the field. This very modest development became stagnant in the early 1970's and was followed by a rapid decline. This exceptional fate of a branch of organometallic chemistry is only partly due to the very limited number of potential application~ of beryllium and its compounds. The compounds of this element are, in principle, at least as interesting and intriguing to scientists as those of other metals in the Periodic Table. No doubt the main reason for the apparent ban of all experimental organoberyllium chemistry is to be found in the established, and alleged, hazardous properties of beryllium compounds. Although similar hazards have been established for other organometallics where active research is still in process, e. g. , mercury and lead, these observations were absolutely lethaI for organoberyllium research.
Häftad, Engelska, 2013
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Häftad, Engelska, 2013
809 kr
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The 3rd supplement continues the updating of the original 20 volumes on boron compounds published between 1974 and 1979. The first supplement consisting of 3 volumes covered all the literature uniformly up to the end of 1977, whereas the two volumes of the 2nd supplement have extended the literature coverage of boron compounds to 1980 and the four volumes of the 3rd supplement to 1984. The present volume continues the description of boron compounds with halogens, presenting those with chlorine, bromine and iodine. The compounds with chalcogens are completed here along with those of boron with S, Se, Te and Po. The final chapter on carboranes contains the carboranes themselves, together with metallacarboranes, and in the last section a description of carborane-containing polymers, mostly derived from the three isomeric dicarbadodecarboranes. Volume 4 of the 3rd supplement brings this supplement series to an end. It will be supplemented by a separately appearing index volume, which contains all the boron compounds dealt with in volumes 1 - 4 of this supplement series.
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A broad coverage of boron topics is provided. Structural elucidations and convenient routes to useful hydroboration reagents are presented as well as boron compounds used for medical purposes. Special attention is devoted to theoretical studies and calculations on small boron-hydrogen and boron-noble gas species including molecules like BH, which are rather favorite subjects of theoreticians for testing various methods of calculation.
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The present issue, Volume 2 of "Boron Compounds" 4th Supplement of the Gmelin Hand book, updates the previous issues by reporting the literature on boron-oxygen systems published up to 1988. For some important recent developments literature is covered through mid-1992; this concerns, for example, the compounds ~-Ba3[B306h and U[B305J which became of interest as materials with nonlinear optical properties. The volume directly com plements the earlier "Boron Compounds" 3rd Supplement Volume 2. In the original literature, alternative formulations are frequently used for the same com pound. This is especially true for many borates. Often, these species are neither completely heteropolar nor covalent, and an experimentally based decision has not been made. Hence, the use of brackets does not necessarily reflect a truly salt-like character. Volume 1 (systems with hydrogen and noble gases) of this particular supplement will be published subsequently, whereas Volume 3a (boron and nitrogen), Volume 3b (boron and nitrogen, boron and fluorine), and Volume 4 (boron compounds containing Cl, Br, I, S, Se, and Te, as well as a section containing carboranes) have already been published. All volumes of the 4th supplement will be augmented by a formula index. The IUPAC nomenclature is generally adhered to; thf means tetrahydrofuran; and occa sionally additional abbreviations for compounds are explained in the text. Positive signs for chemical shifts of the NMR signals indicates downfield shifts from the references, usually internal (CH3)4Si for olH and 013C with others being specified.
Häftad, Engelska, 2013
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The GmeLin FormuLa Index and its First SuppLement covered those voLumes of the Eighth Edition of the GmeLin Handbook which had been issued up to the end of 1979. The present Second SuppLement updates the Index by incLusion of the voLumes which appeared up to the end of 1987. With this Second SuppLement aLL compounds described in the GmeLin Handbook of Inorganic Chemistry in the period between 1924 and 1987 can be Located. The basic structure of the FormuLa Index remains the same as in the previous editions. Computer techniques were empLoyed in the preparation and print of the Second SuppLe- ment. The data acquisition, sorting, and further data handling were performed with the aid of a series of computer programs deveLoped by staff members of the former" Online Group" of the GmeLin Institute, now at ChempLex GmbH, and by the printer" UniversiHits- druckerei H. StOrtz AG, Wurzburg". Whereas the Handbook itself wiLL continue to appear in printed form, the present Second SuppLement of the Index is intended to be the Last one issued in print.The cumuLated contents of the Index and its SuppLements are contained in the GmeLin FormuLa Index (GFI) database which is avaiLabLe to the scientific community via STN. This database wiLL be updated annually to incLude the published Handbook voLumes.
Häftad, Engelska, 2013
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Häftad, Engelska, 2013
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This fourth volume on organoantimony compounds describes pentavalent antimony com- pounds of the type R and R . The R denotes an organic group bonded by carbon 3SbX2 3Sb=X to the antimony atom. X represents a group, inorganic or organic, which is bonded to the antimony by an atom other than carbon. The X atoms in R may be part of a 3SbX2 ring system. In the case of bidentate X ligands like 02- , S2-, SO~-, CO~-, and others, the compounds are placed with the mononuclear RssbX compounds. 2 I once again thank Dr. Margot Becke and Dr. Ekkehard Fluck for the stimulus that led to this book. To the editor of the former volumes, Dr. Hubert Bitterert gratitude and memory are due. I especially thank Drs. Ulrich Kruerke and Marlies Mirbach for editing this volume, Mrs. Ursula Hettwer for systematically arranging the compounds, and Mr. Edgar Rudolph for preparing the index. Last but not least I thank my wife Sigrid for putting my handwritten manuscript into legible form.Gramschatz, Altes Forsthaus, June 1986 Markus Wieber x Explanations, Abbreviations, and Units Many eompounds in this voLume are presented in tabLes in whieh abbreviations are used and the units are omitted for the sake of eoneiseness. This neeessitates the foLLowing ctarifieation.
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This fifth volume on organoantimony compounds continues the description of pentavalent antimony compounds and concludes the entire series. The treatment of pentavalent compounds with three Sb-C bonds began in Part 4 with the RSbX type and is now completed with types RSb(X)Y, RR'SbX , RR'Sb(X)Y, 3 2 3 2 2 2 RR'R"SbX (Section 2.5.1) and the corresponding bi- and trinuclear compounds (Sec- 2 tions 2.5.2, p.87, and 2.5.3, p. 132). R, R', and R" denote different organic groups bonded through carbon to the antimony atom. X and Y represent inorganic or organic groups that are bonded to antimony by an atom other than carbon. R, X, and/or Y can also be chelating ligands. The remaining part of the volume completeLy covers all pentavalent antimony compounds containing two Sb-C bonds (RSbX , RSb(X )Y, RR'SbX , RR'Sb(X )Y, bi- and tetranucLear 2 3 2 2 3 2 compounds, Chapter 2.6, p. 134) and those containing one Sb-C bond (RSbX , RSb(X )Y, 4 3 RSb(X)Y , bi- and trinucLear compounds, Chapter 2.7, p. 237). These compounds form ad- 2 2 ducts with Lewis bases (symbol D) and form many ionic compLexes by the addition of saLts such as amine hydrochLorides (symbol MZ).The adducts and ionic compLexes are described immediately after the parent substances. The volume concludes with an Empirical Formula Index (p. 318) and a Ligand Formula Index (p. 357).
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The present volume of the Gmelin thorium series describes the solid thorium-carbon compounds with the exception of the carbides and coordination compounds of the type 4 ThAn· X B, where B is a neutral ligand. The complex equilibria of the Th + ion with C-containing complexing agents are treated in the ThD1 volume. A first look into this volume demonstrates that a very large number of ThlV complexes has 4 been prepared. This may be explained by the fact that the Th + ion is the largest tetravalent ion of the periodic table. Therefore, the preparation of complexes with, e. g. , multidentate ligands can give a well-established picture of the coordination number as a function of charge and ionic radius. However, there are very few modern and updated comprehensive treatments of such data. Many compounds described in this volume are characterized by no other means than analytical composition and IR spectra (whereby IR spectra of organic ThlV salts mostly give information only on the ligand). Besides thorium carbonate and carbonato complexes, which are relevant for the environmental behaviour of this radioactive element and some organic complexes like oxalates, which are used in the field of analytical and separation chemistry nearly all other compounds described here are practically only of scientific interest. On the other hand in order to have scientifically reliable data, a very large part of these compounds needs further investigation and characterization.
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The present volume in the organogermanium series describes mononuclear compounds containing only germanium-carbon and germanium-hydrogen bonds (Chapter 1.3). Germanium hydrides with other additional non-carbon ligands, such as halogen or oxygen bonded groups, appear in later chapters according to the Gmelin principle of the last posi tion. Compounds with Ge-H and Ge-O bonds have already been described in Volume 5, Section 1.5.1.4, pp. 50/62. The present volume covers the literature to the end of 1992 and includes many references up to 1994. The nomenclature recommended by IUPAC has been generally adhered to. However, compound names were largely avoided, as most of the compounds are presented in tables and are only identified by their formulas. Many of the data in the tables appear in abbreviated form without units; general explanations are given on pp. X/XI. The volume contains an empirical formula index (p. 327) and a ligand formula index (p.341). The editor wishes to express his gratitude to the former author, Professor J. E. Drake, and to Professor J. Satge for his kind advice and fruitful collaboration. Thanks are due also to Dr. A. R. Pebler for editing the English text and to Mr. H.-G. Karrenberg for drawing the numerous formulas and molecular structures.
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This volume C 3, as a part of the Gmelin "Thorium" Handbook, Series C, describes the thorium-nitrogen compounds. Included are compounds both of technological importance like the nitrides and the nitrates and those of merely scientific interest, such as amides and related compounds. However, due to the decreasing technical importance of the nuclear thorium fuel cycle, especially with the advanced fuels like the nitride ThN, in recent years, the thorium compounds with nitrogen have been investigated much less extensively than the correspond ing uranium compounds. In order to have the data for the Th-N-X systems accumulated in one specific volume, the decision was made to publish this volume without incorporating other Th systems. ThN is the compound with the lowest N :Th ratio. In addition to its (former) nuclear interest due to its thermal and radiation stability, it has many very interesting physicochemical properties. Thorium nitrate, the other well-investigated compound, is of importance because it is (in the form of an adduct with tri-n-butylphosphate) the extracted compound when burnt-up thorium fuels are reprocessed. Despite the wealth of accumulated data on the chemical and physicochemical properties of the compounds discussed, the knowledge of the compounds and of the systems is far from satisfactory - it must be deepened and improved in further studies. I would like to thank the competent authors for their critical contributions as well as the Gmelin-Institute for the excellent cooperation provided, especially Prof. Dr. Fluck and Dr. Keim, the editor-in-chief of this volume.
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"Nitrogen" Suppt. Vol. B 1 describes the compounds of nitrogen with noble gases and, in the major part, binary compounds composed of one nitrogen atom and hydrogen. Nitrogen hydrogen compounds with two and more nitrogen atoms are covered in "Nitrogen" Suppt. Vol. 82. There is some information on various nitrogen-noble gas species, to a large extent because of the interest in their bonding behavior. Experimental data have been obtained chiefly for some singly charged cations, particularly those formed by argon Like ArN + and ArNi. The existence of others has only been established by mass spectrometry. The binary compounds of nitrogen and hydrogen comprise NH, NH , NH , NH , the corre 2 4 5 sponding ions, and some adducts. NH and NH1 are not treated. The predominant part 3 of the volume covers the description of the molecules NH and NH . 8oth species are present 2 in photolytic processes in the atmosphere. They play an essential role in combustion systems regardless of whether the nitrogen stems from the nitrogen-containing fuel or from the air. Thus, much work has been devoted to the understanding of the nitrogen chemistry in combustion and in the atmosphere. The production and detection methods as weiL as the reactions have been comprehensively described. ln addition detailed information is given on the spectral behavior, the knowledge of which is important for detecting the mole cules and for studying their kinetics.
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"Nitrogen" SuppL. Vol. 82 continues the description of binary compounds composed of nitrogen and hydrogen (nitrogen hydrides). While" Nitrogen" SuppL. Vol. 81 covers mono- nitrogen compounds, the present volume comprises compounds having two, three, four, or more nitrogen atoms. Hydrazine, N H , and its ions N2Ht and N2H~+ were not included. 2 4 (Reference is made to a voluminous monograph: E.W. Schmidt, Hydrazine and its Deriva- tives: Preparation, Properties, Applications, Chichester 1984, 1088 pages.) Among the dinitrogen compounds, the diazenyl cation, N H+, has been extensively inves- 2 tigated, especially in regards to spectroscopic and kinetic properties, because of its occur- rence in interstellar space. Chemically well-characterized are diazene, N H , the simplest 2 2 unsaturated nitrogen hydride which is used as a hydrogenation reagent, and the hydrazyl radical, N H , which is frequently present as an intermediate during the formation and 2 3 decay of nitrogen-hydrogen compounds. The major portion of this volume is taken up by hydrogen azide or hydrazoic acid, HN , the first member in the series of trinitrogen compounds.Known to be highly explosive 3 in pure form, it can be safely handled when diluted. Thus, a great deal of information is available mainly on its properties as a chemical reagent and its decomposition processes.
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The present volume, "Fluorine" Suppt. Vol. 4, covers the oxygen compounds of fluorine and the binary fluorine-nitrogen compounds. In the first part "Fluorine and Oxygen", oxygen fluorides OnF m are described in the order of decreasing F: 0 ratio. It finishes with a description of hyperfluorous acid HOF. The second part "Fluorine and Nitrogen" deals with the binary fluorine-nitrogen com pounds. They are subdivided on the basis of the number of nitrogen atoms per molecule. Thus, species such as NFt, NF , NF , and NF are considered first followed by the dinitrogen and 3 2 trinitrogen fluorides NF, NF, and NF and related ions. 2 4 2 2 3 The other compounds under the heading "Fluorine and Nitrogen", the fluorine-nitrogen hydrogen and the fluorine-nitrogen-oxygen(-hydrogen) compounds, will be covered in "Fluorine" Suppt. Vol. 5. Intense development in the field of inorganic fluorine-oxygen and fluorine"nitrogen chem istry began in the middle of the 1950s when in less than a decade numerous previously unknown compounds and a great deal of new information were produced. Research in this field was strongly stimulated by interest in these compounds as potential high-energy oxi dizers for rocket fuels. That is also the reason why much of the pertinent chemical information is found in patent Iiterature and U.S. Government contractor reports.
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The present volume, Thorium C5, deals with the compounds of thorium and sulfur, selenium, tellurium, and boron, as well as with oxoacid compounds of the three chalcogen elements. Thorium borates have already been treated in Thorium C2. In contrast to the corresponding compounds of uranium the thorium sulfides, etc. , do not show any nuclear or other technological application; they are only of academic interest, despite some very interest ing electronic properties, especially of the 1 : 1 compounds. The thorium-sulfur and the thorium boron systems in particular were studied in detail, so that we have a clear picture of them, whereas there are still a lot of open questions in the systems Th-Se and Th-Te - not very different from other metal chalcogenide systems. Thorium sulfates are of some technological importance because they are formed in solution during recovery of thorium from monazite by sulfuric acid leaching. The very detailed and critical treatment of the chemical and physical properties of the compounds discussed also enables us to find gaps still remaining in our knowledge and thus to initiate new research in this field. I want to thank the two authors, Dr. Horst Wedemeyer (Karlsruhe) and Dr. David Brown (Harwell), for their excellent contributions, the "Literaturabteilung" of the Karlsruhe Nuclear Research Center for its help in providing reports and other documents difficult to procure, as well as the staff of the Gmelin-Institute, especially to Dr. K. -C.
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The present volume describes acyclic Sulfur-nitrogen compounds with sulfur of the oxida- tion number II. The first chapter deals with sulfur imide (S=NH), N-organyl-sulfur imides (S=NR, R = or- ganyl), and metal complexes of sulfur imides. N-Organyl-sulfur imides have not been isolated, but they can be trapped, for example, by cycloaddition and stabilized by coordination to transi- tion metals. 11 The following chapter present a detailed survey of other 8 -N compounds with one- coordinate sulfur, e.g., dithionitrous acid (S=N-SH) and derivatives, the salts of the dithionitryl ion (1 +) ([S=N=S]+), and N-thionitroso-diorganyl-amines (S=NNR , R = organyl). Only the reac- 2 tions of [S=N=S]+ AsF5, among the known [S=N=S]+ salts, have been extensively studied. Cycloadditions with alkenes and triple bonded compounds produce 1 ,3,2-dithiazolium salts and their derivatives. S=NN(CH )z and S=NN(C H )z form transition metal complexes. The 3 6 5 Iigand is coordinated via the S atom in a monodentate manner.
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PF3, (CH3)3SiCl -> (CH3)3SiF, and RC(O)Cl -> RC(O)F. Others include the conversion of (C6H5)3P into (C6H5)3PF2 and of (R3NC(S)S)2 into R2NCF3, R=alkyl. In organic chemistry, fluorides are easily accessible from alcohols, geminal fluorides RR'CF2 from the respective aldehydes or ketones, and acyl fluorides RC(O)F from carboxylic acides by using DAST. Because DAST is easy to handle and gives clean reactions in syntheses, this Gmelin volume devotes much space to the description of the chemical and physical properties od DAST.