This volume C 1 is the first supplement volume to "Phosphor" C which was published in 1965 and covers the compounds of phosphorus. Starting with the binary species formed between phosphorus and hydrogen, the present volume deals with the neutral mononuclear compounds PH through PH ; the ions featuring the same stoichiometric composition are s covered in separate sections. PH and PH are the major initial gaseous decomposition products of PH and, thus, also 2 J intermediates in many of its gas-phase reactions. Both molecules and their ions have been thoroughly investigated by a variety of modern, high-resolution spectroscopic methods during the last three decades. The coverage of their physical, and mostly molecular, properties re presents the largest part of the first two chapters (PH and ions pp. 2 to 47; PH and ions pp. 47 2 to 111). PH is the only compound described in this volume which is thermally stable under normal J conditions. It is the phosphorus analog of ammonia, but exhibits, however, a quite different chemical behavior towards most elements and compounds. The majority of its physical, and in particular spectroscopic, properties have been determined in great detail since the sixties, partially in regard to spectroscopic investigations of the atmospheres of the outer planets.
This fourth volume of the Supplement Series supplying the Main Volumes of the series "Perfluorohalogenoorgano Compounds of Main Group Elements" (Part 1 to 9) covers the heterocyclic compounds of nitrogen as the last main group element of this series. Compounds of the elements of main group 1 to 4, 6 (without 0), and of P, As, Sb, Bi, and I are presented in the Supplement Volumes 1 to 3. Concept, organization, and selection as to coverage of the material are the same as in the preceeding volumes. Title compounds are either newly synthesized ones or those compounds already referred in the Main Volume Parts 5 and 6 for which new facts have been published. I wish to thank Prof. Dr. Dr. h. c. E. Fluck and his co-workers for their excellent cooperation and many colleagues for providing reprints and patents. One of us (U. Niemann) thanks Philips GmbH Forschungslaboratorium Aachen for generous support. November 1987 Bochum, A. Haas x Table of Contents Page 1 Three-Membered Perfluorohalogenoorgano Nitrogen Heterocycles 1-1 Formation and Preparation . . . . . . . . . . . 1-1.1 Three-Membered Heterocycles with One N Atom.
The volume is concerned exclusively with all the binary species formed between the elements silicon and fluorine such as SiF, SiF2, SiF3, SiF4, and Sif62-. Most of the volume, i.e. 144 pages, is devoted to the description of the well known physical and chemical properties of the SiF4 as well as to its preparation. This is followed in length by the report on SiF2 with its interesting chemistry, along with a section on the diatomic radical SiF. Species with fivefold and sixfold coordination of silicon are exemplified by SiF5- and by the well known SiF62-. Interestingly, the detailed models for describing the bonding situation in both ions are still a matter of discussion. While for Si2F6 most of the basic data are known, information on the chemical and physical properties of the higher members of the acylic perfluorosilanes, SinF2n+2, is scarce. All available information on the unstable cyclic perfluorosilanes of composition (SiF2)n and some even more exotic species is also included.
Some years ago the Gmelin Institute started to supplement the volumes on halogens and halogen compounds. For the elements chlorine and fluorine these supplementary volumes have already been finished. For the element bromine the volume A 1 is also available. Now the volume B 1 will be published starting with the description of the compounds of bromine. The present volume describes the compounds of bromine with rare gases and with hydrogen. The volume is dominated by the description of HBr and its aqueous solution, hydrobromic acid. Chemical and physical properties of the diatomic molecule HBr are extremely well studied by modern methods. Thus detailed descriptions are given of gas-phase properties, spectra, and properties of condensed phases. Emphasis is laid on elementary reaction processes such as energy transfer and single reaction steps for HBr formation and decomposition. These studies have become classics of modern reaction kinetics. Likewise, elementary reactions of HBr and Br- with nonmetallic compounds are described comprehensively.
This volume C 1 is the first supplement volume to "Phosphor" C which was published in 1965 and covers the compounds of phosphorus. Starting with the binary species formed between phosphorus and hydrogen, the present volume deals with the neutral mononuclear compounds PH through PH ; the ions featuring the same stoichiometric composition are s covered in separate sections. PH and PH are the major initial gaseous decomposition products of PH and, thus, also 2 J intermediates in many of its gas-phase reactions. Both molecules and their ions have been thoroughly investigated by a variety of modern, high-resolution spectroscopic methods during the last three decades. The coverage of their physical, and mostly molecular, properties re presents the largest part of the first two chapters (PH and ions pp. 2 to 47; PH and ions pp. 47 2 to 111). PH is the only compound described in this volume which is thermally stable under normal J conditions. It is the phosphorus analog of ammonia, but exhibits, however, a quite different chemical behavior towards most elements and compounds. The majority of its physical, and in particular spectroscopic, properties have been determined in great detail since the sixties, partially in regard to spectroscopic investigations of the atmospheres of the outer planets.
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.
The volume describes the chemical and physical properties of the approximately 80 known bromine compounds and ions which contain oxygen and/or nitrogen, and which may include hydrogen as well. The class of bromine-oxygen and bromine-oxygen-hydrogen compounds comprises several well-known species. Their description accounts for approximately three-quarters of the volume. The BrO radical and the BrO3 ion are the most and best studied among all binary bromine-oxygen species. BrO was recently recognized to play a role in some reaction sequences depleting the ozone concentration in the stratosphere. Bromate-ion-driven chemical oscillator systems have attracted much interest in recent decades. Thus data on single reaction steps which involve BrO3, BrO2, and the oxoacides of bromine - HBrO, HBrO2, and HBrO3 - are reviewed in detail; a comprehensive description of the oscillating systems, however, is beyond the scope of this volume. The remaining one-quarter of the volume is devoted to bromine-nitrogen and bromine-nitrogen-oxygen compounds. Bromine azide and nitrosyl bromide are the most comprehensively studied of these, accounting for almost half of this section.
This third volume of the Supplement Series supplying the Main Volumes of the series "Perfluorohalogenoorgano Compounds of Main Group Elements", Part 1 to 9, completes the treatment of the compounds of the Main Group VI elements. It covers sulfur(IV) compounds, sulfonic acids, sulfonic anhydrides, and sulfonates, sulfur(VI) oxides, sulfonyl nitrogen compounds, sulfonyl halides, sulfur(VI) halides, and the compounds of selenium and tellurium. It also includes the perfluorohalogenoorgano compounds of iodine in oxidation states higher than one and contains a formula index for the Supplement Volumes 1, 2, and 3. The Supplement Series will be concluded by the description of the nitrogen compounds. Concept, organization, and selection as to the coverage of the material are the same as in the Main Volumes. Title compounds are newly synthesized ones as well as those compounds already referred to in the Main Volumes and for which new facts have been published. Conventions as to the presentation of the data are given in the prefaces of the Main Volumes. In contrast to the convention for NMR chemical shifts used previously, chemical shifts downfield from the standard are designated as positive, according to the recommendations of the IUPAC Commission on Molecular Structure and Spectroscopy (Pure and Applied Chemistry 29 [1972]625/8, 45 [1976] 217/9). I wish to thank Prof. Dr. Dr. h.c. E. Fluck and his co-workers for their excellent cooperation. I also wish to take the opportunity to express my appreciation to colleagues who assisted me by providing reprints and patents.
This fourth volume of the Supplement Series supplying the Main Volumes of the series "Perfluorohalogenoorgano Compounds of Main Group Elements" (Part 1 to 9) covers the heterocyclic compounds of nitrogen as the last main group element of this series. Compounds of the elements of main group 1 to 4, 6 (without 0), and of P, As, Sb, Bi, and I are presented in the Supplement Volumes 1 to 3. Concept, organization, and selection as to coverage of the material are the same as in the preceeding volumes. Title compounds are either newly synthesized ones or those compounds already referred in the Main Volume Parts 5 and 6 for which new facts have been published. I wish to thank Prof. Dr. Dr. h. c. E. Fluck and his co-workers for their excellent cooperation and many colleagues for providing reprints and patents. One of us (U. Niemann) thanks Philips GmbH Forschungslaboratorium Aachen for generous support. November 1987 Bochum, A. Haas x Table of Contents Page 1 Three-Membered Perfluorohalogenoorgano Nitrogen Heterocycles 1-1 Formation and Preparation . . . . . . . . . . . 1-1.1 Three-Membered Heterocycles with One N Atom.
This volume C 1 is the first supplement volume to "Phosphor" C which was published in 1965 and covers the compounds of phosphorus. Starting with the binary species formed between phosphorus and hydrogen, the present volume deals with the neutral mononuclear compounds PH through PH ; the ions featuring the same stoichiometric composition are s covered in separate sections. PH and PH are the major initial gaseous decomposition products of PH and, thus, also 2 J intermediates in many of its gas-phase reactions. Both molecules and their ions have been thoroughly investigated by a variety of modern, high-resolution spectroscopic methods during the last three decades. The coverage of their physical, and mostly molecular, properties re presents the largest part of the first two chapters (PH and ions pp. 2 to 47; PH and ions pp. 47 2 to 111). PH is the only compound described in this volume which is thermally stable under normal J conditions. It is the phosphorus analog of ammonia, but exhibits, however, a quite different chemical behavior towards most elements and compounds. The majority of its physical, and in particular spectroscopic, properties have been determined in great detail since the sixties, partially in regard to spectroscopic investigations of the atmospheres of the outer planets.
Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
This fifth volume of the first supplement supplying the Main Volumes of the series Perfluorohalogenoorgano Compounds of Main Group Elements, Part 1 to 9, starts the treatment of the aliphatic and aromatic perfluorohalogenoorgano compounds of nitrogen. Amines, amides, imines, aminooxy derivatives, nitro- and nitroso compounds as well as azides, hydrazines and diazenes among others are described.
This fourth volume of the Supplement Series supplying the Main Volumes of the series "Perfluorohalogenoorgano Compounds of Main Group Elements" (Part 1 to 9) covers the heterocyclic compounds of nitrogen as the last main group element of this series. Compounds of the elements of main group 1 to 4, 6 (without 0), and of P, As, Sb, Bi, and I are presented in the Supplement Volumes 1 to 3. Concept, organization, and selection as to coverage of the material are the same as in the preceeding volumes. Title compounds are either newly synthesized ones or those compounds already referred in the Main Volume Parts 5 and 6 for which new facts have been published. I wish to thank Prof. Dr. Dr. h. c. E. Fluck and his co-workers for their excellent cooperation and many colleagues for providing reprints and patents. One of us (U. Niemann) thanks Philips GmbH Forschungslaboratorium Aachen for generous support. November 1987 Bochum, A. Haas x Table of Contents Page 1 Three-Membered Perfluorohalogenoorgano Nitrogen Heterocycles 1-1 Formation and Preparation . . . . . . . . . . . 1-1.1 Three-Membered Heterocycles with One N Atom.
Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
Gmelin Handbook of Inorganic and Organometallic Chemistry, presently comprising over 600 volumes, is the most comprehensive collection of chemical and physical data of the elements and their compounds in the world. It is Gmelin's first aim to assemble and systematically classify the research findings scattered throughout the innumerable publications of the international primary literature. This vast amount of information is classified on the basis of the chemical elements, which in itself contributes to "user friendliness". A survey of the contents of the Handbook is given in the Complete Catalog (published every second year, with supplements in between), which can, thus, be very helpful when beginning a search. Access to a specific compound becomes even easier through consultation of the Formula Index volumes. For over three years the Gmelin Formula Index (plus the Complete Catalog entries) has been available as an online database, GFI, from STN. Online searches provide for a most comfortable and fast access to the Handbook. GFI is the first constituent of the complete Gmelin database presently under development. Subscribers to the Handbook are entitled to a 50 % discount when searching GFI online.
This fifth volume of the first supplement supplying the Main Volumes of the series Perfluorohalogenoorgano Compounds of Main Group Elements, Part 1 to 9, starts the treatment of the aliphatic and aromatic perfluorohalogenoorgano compounds of nitrogen. Amines, amides, imines, aminooxy derivatives, nitro- and nitroso compounds as well as azides, hydrazines and diazenes among others are described.
Some years ago the Gmelin Institute started to supplement the volumes on halogens and halogen compounds. For the elements chlorine and fluorine these supplementary volumes have already been finished. For the element bromine the volume A 1 is also available. Now the volume B 1 will be published starting with the description of the compounds of bromine. The present volume describes the compounds of bromine with rare gases and with hydrogen. The volume is dominated by the description of HBr and its aqueous solution, hydrobromic acid. Chemical and physical properties of the diatomic molecule HBr are extremely well studied by modern methods. Thus detailed descriptions are given of gas-phase properties, spectra, and properties of condensed phases. Emphasis is laid on elementary reaction processes such as energy transfer and single reaction steps for HBr formation and decomposition. These studies have become classics of modern reaction kinetics. Likewise, elementary reactions of HBr and Br- with nonmetallic compounds are described comprehensively.
The present Supplement Volume Beryllium A 3 continues and completes the description of the physical properties of the element, begun in Supplement Volume A 2, 1991, and also treats the electrochemical behavior of the metal. The unique combination of the Be properties, which was pointed out in Supplement Volume A 2, is also demonstrated in the following chapters of this Volume A 3: 13. Electrical Properties 14. Electronic Properties 15. Optical Properties. Emission and Impact Phenomena 16. Electrochemical Behavior Starting with the electrical properties, Be isarather good electrical conductor in centrast to what might be expected. Superconductivity was studied, especially on films. Quantum effects, which are more pronounced in Be than in most other metals, are the reason for numerous in vestigations of the magnetoresistance and the magnetic-breakdown effect. The basis for many of the characteristic properties is the unique nature of bonding in Be as a consequence of its peculiar electronic structure and the special shape of its Fermi surface which also gave rise to further numerous studies. Detailed cluster calculations were per formed to better understand the bonding in the metal. Regarding the optical properties, the high reflectivity of Be, particularly in the infrared region, makes it attractive for the fabrication of precision optical surfaces (mirrors); it is also useful for solar-collector surfaces in spacecraft applications. Emission and electron-and ion impact phenomena as well as neutron optics are also discussed.
As was announced two years ago, the description of the physical properties of molybde num has now been completed in the present volume up to page 124. Whereas most properties, e.g., the electrical, magnetic, and optical properties, are dealt with in the usual manner, the results of studies of the atom and ion emission had to be presented in a revised form, comprising not only the most recent data but having in mind also the corresponding data for tungsten, which will be represented in a supplement volume now in preparation. The various modes of electron emission have also been studied in great detail. Many more pages (exactly 226 pages, as contrasted to three pages in the Main Volume) were needed to present the electrochemical data for molybdenum, which were published to an astonishingly great extent by Russian workers. The large volume of literature is due to the extensive industrial application of the metaL, cf. "MoLybdän" Erg.-Bd. A 1, 1977, and to its occurrence in various oxidation states. Thus the equilibrium between an Mo eLectrode and Mo ions or between an inert eLectrode and Mo ions is deaLt with in the chapters "Standard PotentiaLs" and "PotentiaLs", whereas kinetics and reaction mechanisms of the reduction and oxidation of Mo ions on a dropping mercury electrode and other inert eLectrodes can be found in the chapter "Polarography/ Voltammetry.
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