230 Topics in Current Chemistry doc

230 Topics in Current Chemistry Editorial Board: A. de Meijere · K.N. Houk · H. Kessler · J M. Lehn S.V. Ley · S.L. Schreiber · J. Thiem · B.M. Trost F. Vögtle · H. Yamamoto D Berlin Heidelberg New York Hong Kong London Milan Paris Tokyo Elemental Sulfur and Sulfur-Rich Compounds I Volume Editor: Ralf Steudel With contributions by B. Eckert · A.J.H. Janssen · A. de Keizer W. E. Kleinjan · I. Krossing · R. Steudel · Y. Steudel M. W. Wong BD The series Topics in Current Chemistry presents crit ical reviews of the present and future trends in modern chemical research. The scope of coverage in- cludes all areas of chemical science including the interfaces w ith related dis- ciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the nonspecialist reader, whether at the university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. As a rule, contributions are specially commissioned. The editors and publish- ers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for Topics in Current Chemistry in English. In references Topics in Current Chemistry is abbreviated Top Curr Chem and is cited as a journal. Springer WWW home page: http://www.springer.de Visit the TCC home page at http://www.springerlink.com ISSN 0340 -1022 ISBN 3-540-40191-1 DOI 10.1007/b12115 Springer-Verlag Berlin Heidelberg New York Library of Congress Catalog Card Number 74-644622 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, re- printing, reuse of illustrations, recitation, broadcasting, reproduction on mi- crofilms or in any other ways, and storage in data banks. Duplication of this publication or parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1965, in its current version, and per- mission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. Springer-Verlag Berlin Heidelberg New York a member of BertelsmannSpringer Science+Business Media GmbH http://www.springer.de  Springer-Verlag Berlin Heidelberg 2003 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: KünkelLopka, Heidelberg/design & production GmbH, Heidelberg Typesetting: Stürtz AG, 97080 Würzburg 02/3020 ra – 5 4 3 2 1 0 – Printed on acid-free paper Volume Editor Prof. Dr. Ralf Steudel Technische Universität Berlin Institut für Chemie / Sekr. C2 Straße des 17. Juni 135 10623 Berlin, Germany E-mail: steudel@s chwefel.chem.tu-berlin.de Editorial Board Prof. Dr. Armin de Meijere Institut für Organische Chemie der Georg-August-Universität Tammannstraße 2 37077 Göttingen, Germany E-mail: ameijer1@uni-goettingen.de Prof. Dr. Horst Kessler Institut für Organische Chemie TU München Lichtenbergstraße 4 85747 Garching, Germany E-mail: kessler@ch.tum.de Prof. Steven V. Ley University Chemical Laboratory Lensfield Road Cambridge CB2 1EW, Great Britain E-mail: svl1000@cus.cam.ac.uk Prof. Dr. Joachim Thiem Institut für Organische Chemie Universität Hamburg Martin-Luther-King-Platz 6 20146 Hamburg, Germany E-mail: thiem@chemie.uni-hamburg.de Prof. Dr. Fritz Vögtle KekulØ-Institut für Organische Chemie und Biochemie der Universität Bonn Gerhard-Domagk-Straße 1 53121 Bonn, Germany E-mail: voegtle@uni-bonn.de Prof. K.N. Houk Department of Chemistry and Biochemistry University of California 405 Hilgard Avenue Los Angeles, CA 90024-1589, USA E-mail: houk@chem.ucla.edu Prof. Jean-Marie Lehn Institut de Chimie UniversitØ de Strasbourg 1 rue Blaise Pascal, B.P.Z 296/R8 67008 Strasbourg Cedex, France E-mail: lehn@chimie.u-strasbg.fr Prof. Stuart L. Schreiber Chemical Laboratories Harvard University 12 Oxford Street Cambridge, MA 02138-2902, USA E-mail: sls@slsiris.harvard.edu Prof. Barry M. Trost Department of Chemistry Stanford University Stanford, CA 94305-5080, USA E-mail: bmtrost@leland.stanford.edu Prof. Hisashi Yamamoto School of Engineering Nagoya University Chikusa, Nagoya 464-01, Japan E-mail: j45988a@nucc.cc.nagoya-u.ac.jp Topics in Current Chemistry Also Available Electronically For all customers with a standing order for Topics in Current Chemistry we offer the electronic form via SpringerLink free of charge. Please contact your librarian who can receive a password for free access to the full articles by registration at: http://www.springerlink.com If you do not have a standing order you can nevertheless browse through the table of contents of the volumes and the abstracts of each article by choosing Topics in Current Chemistry within the Chemistry Online Library. – Editorial Board – Aims and Scope – Instructions for Authors Preface Despite more than 200 years of sulfur research the chemistry of elemental sulfur and sulfur-rich compounds is still full of “white spots” which have to be filled in with solid knowledge and reliable data. This situation is particu- larly regrettable since elemental sulfur is one of the most important raw ma- terials of the chemical industry produced in record-breaking quantities of ca. 35 million tons annually worldwide and mainly used for the production of sulfuric acid. Fortunately, enormous progress has been made during the last 30 years in the understanding of the “yellow element”. As the result of extensive interna- tional research activities sulfur has now become the element with the largest number of allotropes, the element with the larges t number of binary oxides, and also the element with the largest number of binary nitrides. Sulfur, a typical non-metal, has been found to become a metal at high pressure and is even superconducting at 10 K under a pressure of 93 GPa and at 17 K at 260 GPa, respectively. This is the highest critical temperature of all chemical elements. Actually, the pressure-temperature phase diagram of sulfur is one of the most complicated of all elements and still needs further investigation. Sulfur compounds have long been recognized as important for all life since sulfur atoms are components of many important biologically active molecules including amino acids, proteins, hormones and enzymes. All these compounds take part in the global geobiochemical cycle of sulfur and in this way influence even the earths climate. In interstellar space, on other planets as well as on some of their moons have elemental sulfur and/or sulfur compounds also been detected. The best known example in this context is probably Iupiters moon Io, first observed by Galileo Galilei in 1610, which according to modern spectro- scopic observations made from the ground as well as from spacecrafts is one of the most active bodys in the solar system with quite a number of sulfur volca- noes powered by sulfur dioxide and spraying liquid sulfur onto the very cold surface of this moon. The general importance of sulfur chemistry is reflected in the long list of monographs on special topics published continuously, as well as in the huge number of original papers on sulfur related topics which appear every year. Reg- ularly are international conferences on organic and inorganic sulfur che mistry held, and specialized journals cover the progress in these areas. In Volumes 230 and 231 of Topics in Current Chemistry eleven experts in the field report on the recent progress in the chemistry and physics of elemental sulfur in the solid, liquid, gaseous and colloidal form, on oxidation products of elemental sulfur such as polyatomic sulfur cations and sulfur-r ich oxides which both exhibit very unusual structures, on classical reduction products such as polysulfide dianions and radical anions as well as on their interesting coordina- tion chemistry. Furthermore, the long homologous series of the polysulfanes and their industrial significance are covered, and novel methods for the removal of poisonous sulfur compounds from wastegases and wastewaters in bioreactors taking advantage of the enzymatic activities of sulfur bacteria are reviewed. In addition, the modern ideas on the bonding in compounds containing sulfur-sul- fur bonds are outlined. The literature is covered up to the beginning of the year 2003. A list of useful previous reviews and monographs related to the chemistry of sulfur-rich com- pounds including elemental sulfur is available on-line as suplementary material to these Volumes. As the guest-editor of Volumes 230 and 231, I have worked for 40 years in basic research on sulfur chemistry, and I am grateful to my coworkers w hose names appear in the references, for their skillful experimental and theoretical work. But my current contributions to these Volumes would not have been pos- sible without the continuous encouragement and assistance of my wife Yana who also took care of some of the graphical work. The constructive cooperation of all the co-authors and of Springer-Verlag, Heidelberg, is gratefully acknowl- edged. Berlin, April 2003 Ralf Steudel VIII Preface Contents Solid Sulfur Allotropes R. Steudel · B. Eckert . . 1 Liquid Sulfur R. Steudel . . . 81 Speciation and Thermodynamics of Sulfur Vapor R. Steudel · Y. Steudel · M. W. Wong 117 Homoatomic Sulfur Cations I. Krossing . . 135 Aqueous Sulfur Sols R. Steudel . . . 153 Biologically Produced Sulfur W. E. Kleinjan · A. de Keizer · A. J. H. Janssen 167 Author Index Volumes 201–230 189 Subject Index 199 Contents of Volume 231 Elemental Sulfur and Sulfur-Rich Compounds II Volume Editor: Ralf Steudel ISBN 3-540-40378-7 Quantum-Chemical Calculations of Sulfur-Rich Compounds M. W. Wong Molecular Spectra of Sulfur Molecules and Solid Sulfur Allotropes B. Eckert · R. Steudel Inorganic Polysulfanes H 2 S n with n>1 R. Steudel Inorganic Polysulfides S n 2– and Radical Anions S n – R. Steudel Polysulfido Complexes of Main Group and Transition Metals N. Takeda · N. Tokitoh · R. Okazaki Sulfur-Rich Oxides S n O and S n O 2 R. Steudel [...]... sulfur is usually obtained in a microcrystalline (random coil) state and is often called m-sulfur or Sm These polymeric forms seem to consist, in principal, of the same type of helical molecules In addition to long chains the polymeric allotropes are likely to contain also large sulfur rings in differing concentrations Another way to indicate the polymeric nature of sulfur chains is to use the symbol... words, polymeric sulfur is a mixture of chains of differing lengths and rings of differing sizes rather than a pure compound The nature of the chain-terminating endgroups is unknown In some cases crystalline phases have been obtained and the molecular structures were determined by X-ray crystallography These phases are known as Sw1 and Sw2 and consist of helical chains (catenapolysulfur); they will be discussed... authors give differing maximum polymer concentrations) [49] The quenching can be achieved by pouring the sulfur melt into water or, better, into liquid nitrogen [19, 43] as well as by blowing a thin stream of liquid sulfur by a jetstream of cold air against a sheet of aluminum on which the melt solidifies immediately as a thin film [50] After quenching and extraction the polymeric sulfur is initially amorphous... 90 at the S-S bonds in the case of a “free” chain corresponding to a minimum of configurational energy [54] This model explains why chains of cumulated S-S bonds exhibit a three-dimensional zig-zag conformation rather than a planar configuration In consequence, a large number of quite different cyclic and chain-like molecules is, in principal, possible Ring closure of a sulfur chain usually causes deviations... hundred gram) is heated electrically to about 200 C for 5– 10 min or longer and is then allowed to cool to 140–160 C within ca 15 min As soon as the melt has become less viscous, it is poured in as thin a stream as possible into liquid nitrogen in order to quench the equilibrium The boiling nitrogen ruptures the melt into small pieces resulting in a yellow powder The liquid nitrogen is decanted off this... depolymerization), filtration, and drying in nitrogen gas Common stabilizers [58] are certain olefins R2C=CH2 like a-methylstyrene which obviously react with the chain-ends (probably -SH) of the sulfur polymer and in this way hinder the formation of rings by a tail-bites-head reaction In this industrial process the polymer forms from reactive small sulfur molecules present in sulfur vapor [59] which are unstable... obtained by quenching liquid sulfur from 350 C to 20 C (in cold water) and stretching the fibers obtained in the direction of their axes According to an X-ray diffraction study, this “fibrous” sulfur consists of helical polymeric sulfur chains (Sw, see below) which form pockets filled with S8 molecules as the monoclinic gallotrope [31] 8 Ralf Steudel · Bodo Eckert 2.1.1.4 Preparation of S9 In principle,... experimentally by several techniques [76, 87, 88] 2.2.1.3.2 Monoclinic b-S8 This allotrope is usually obtained by heating of powdered a-S8 to about 369 K In single crystals of a-S8 the transformation is kinetically hindered, for example due to the absence of impurities introduced by grain boundaries Another way to obtain b-S8 is by slow cooling of molten sulfur, or by crystallization from organic solvents... known in most cases, this does not apply to all of the high-pressure forms Therefore, in the following the two groups are described in separate sections of this chapter The allotropes prepared at ambient pressure can also be grouped by their molecular structures depending on whether homocyclic rings or chains of indefinite length are the constituents of the particular phase At present, the following... which eliminate I2 intramolecularly with ring closure to S20 2.1.2 Allotropes Consisting of Long Sulfur Chains (Polymeric Sulfur: Sm , Sy and Sw) Those forms of elemental sulfur which are insoluble even in carbon disulfide at 20 C have been termed as polymeric sulfur These materials consist of chain-like macromolecules but the additional presence of large rings Sn (n>50) is very likely In other words, . supplementary information. Papers are accepted for Topics in Current Chemistry in English. In references Topics in Current Chemistry is abbreviated Top Curr Chem and is cited as a journal. Springer WWW. j45988a@nucc.cc.nagoya-u.ac.jp Topics in Current Chemistry Also Available Electronically For all customers with a standing order for Topics in Current Chemistry we offer the electronic form via SpringerLink free of. on organic and inorganic sulfur che mistry held, and specialized journals cover the progress in these areas. In Volumes 230 and 231 of Topics in Current Chemistry eleven experts in the field report