Dieter Koschel – författare

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.

"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.

"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.

"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.

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.

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 volume describes the isotopes, atoms, atomic ions, molecules, and clusters of the six platinum group elements Ru, Rh, Pd, Os, Ir, and Pt. It starts with a compilation of the properties of the isotopes, followed by the description of the formation and separation of the radioactive isotopes. The chapters on the atoms and atomic ions deal with the configuration of the outer-shell electrons, manifested by optical terms and spectra, ionization energy, and electron affinity, as weil as with the energy levels of the inner-shell electrons, manifested by X-ray spectra and Auger electron spectra. The last section gives information on the formation and the physical properties of the plati­ num group molecules and clusters. Most of the contributions are written by extern al experts (for details, see the back of the titte page). One of the authors (Prof. Y. Cauchois) thanks Dr. M. Othmane for his constant and efficient cooperation in the treatment of the drafts and the checking of the proofs. Frankfurt am Main, January 1989 Dieter Koschel XI Table 0'' Contents Page 1 Ru, Rh, Pd, Os, Ir, and Pt Isotopes 1.1 Introductory Remarks . . . . .