1 3 2 Hel 10 I Ne 18 Ar I 36 Kr I 54 Xe I 86 Rn I H .. ~ 2 5 6 7 8 a I I H 9 F 17 Cl 35 Br 513 85 At8 8 0 3 16 s 9 34 Se 10 52 Te II 84 Po 12 71 Lu 03 71 Lr 1 7 N 4 15 p 16 33 As 17 51 Sb 18 :r 19 70 Yb 02 71 No 1 6 c 14 14 Si 15 32 Ge45 50 Sn 46 82 Pb 47 69 Tm 101 71 Md mbers 5 B 13 13 At35 31 Ga 36 49 ln 37 81 Tl 38 68 Er 100 71 Fm Nu 32 33 34 71 m 30 Zn 48 Cd 80 Hg 67 Ho 99 Es n Syste 29 Cu 60 47 Ag 61 79 Au 62 66 Dy 98 71 Cf e Gmeli 28 Ni 57 46 Pd 65 78 Pt 68 65 Tb 97 71 Bk with th 27 Co 58 45 Rh64 77 Ir 67 64 Gd 9671 Cm ements 26 Fe 59 44 Ru 63 76 Os 66 63 Eu 95 71 Am abte of the El l 24 25 Cr 52 Mn 56 42 43 Mo 53 Tc 69 74 75 w 54 Re 70 61 62 Pm Sm 93 71 94 71 Np Pu l eriodic 23 V 48 41 Nb49 73 Ta 50 105 71 60 Nd 92 55 u P 22 Ti 41 40 Zr 42 72 Hf 43 104 71 59 Pr 91 51 Pa 21 Sc 39 39 y 39 57** La 39 89*** Ac40 58 Ce 90 44 Th 4 Be 26 12 Mg27 20 Ca 28 38 Sr 29 56 30 Ba 88 31 Ra n ides 39 des a ni I H 2 3 Li 20 II Na21 19 * K 22 37 Rb24 55 25 Cs 87 Fr25a k•Lanth **Acli f * ",. f -Q !T "' Cl 3 !!. :;· "' ~ 3 o;· <Cl ;;:· !! !!: ;. "' ä a: .. "' "" ~ n i Gmelin Handbock of lnorganic and Organametallic Chemistry 8th Edition Gmelin Handbook of lnorganic and Organametallic Chemistry 8th Edition Gmelin Handbuch der Anorganischen Chemie Achte, völlig neu bearbeitete Auflage PREPARED Gmelin-Institut für Anorganische Chemie AND ISSUED BY der Max-Planck-Gesellschaft zur Förderung der Wissenschaften Director: Ekkehard Fluck FOUNDED BY Leopold Gmelin 8TH EDITION 8th Edition begun und er the auspices of the Deutsche Chemische Gesellschaft by R. J. Meyer CONTINUED BY E. H. E. Pietsch and A. Kotowski, and by Margot Becke-Goehring Springer-Verlag Berlin Heidelberg GmbH 1994 Gmelin-lnstitut für Anorganische Chemie der Max-Planck-Gesellschaft zur Förderung der Wissenschaften ADVISORY BOARD Min.-Rat Dr. H. Bechte (Bundesministerium für Forschung und Technologie, Sonn), Prof. Dr. K. Dehnicke (Philipps-Universität, Marburg), Prof. Dr. H. Grünewald (Bayer AG, Lever kusen), Prof. Dr. H. Harnisch, Chairman (Hoechst AG, Frankfurt/Main-Höchst), Prof. Dr. H. Nöth (Ludwig-Maximilians-Universität, München), Prof. Dr. H. Ottermanns (Degussa AG, Frankfurt/Main), Prof. Dr. A. Sirnon (Max-Planck-Institut für Festkörperforschung, Stuttgart), Prof. Dr. Dr. h. c. mult. G. Wilke (Max-Planck-lnstitut für Kohlenforschung, Mülheim/Ruhr), Prof. Dr. H. F. Zacher (Präsident der Max-Planck-Gesellschaft, München) DIRECTOR Prof. Dr. Dr. h. c. Ekkehard Fluck CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. U. Krüerke, Dr. A. R. Pebler, Dr. J. F. Rounsaville EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E. h. Margot Becke CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Dr. h. c. Hans Bock, Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.) GMELIN HANDBOOK Or. J. von Jouanne Or. L. Berg, Or. H. Bergmann, Or. J. Faust, J. Füssel, Or. H. Katscher, Or. R. Keim, Oipl.-Phys. 0. Kaschet, Or. A. Kubny, Or. P. Merlet, Or. M. Mirbach, Prof. Or. W. Petz, Or. H. Schäfer, Or. F. A. Schröder, Or. A. Slawisch, Or. W. Töpper Or. R. Albrecht, Or. G. Bär, 0. Barthel, Or. N. Baumann, Or. K. Behrends, Or. W. Behrendt, 0. Benzaid, Dr. R. Bohrer, K. 0. Bann, Oipl.-Chem. U. Boßlet, Or. U. Busch, A.-K. Castro, Oipl. lng. V. A. Chavizon, A. Oittmar, Dipl.-Geol. R. Oitz, R. Oowideit, Or. H.-J. Fachmann, B. Fischer, Or. D. Fischer, Dr. K. Greiner, Dipl.-~ibl. W. Grieser, Dr. R. Haubold, Dipl.-Min. H. Hein, H.-P. Hente, H. W. Herold, U. Hettwer, G. Hoell, Dr. G. Hönes, Or. W. Hoffmann, G. Horndasch, Dr. W. Huisl, Or. M. lrmler, B. Jaeger, Or. R. Jotter, Oipl.-Chem. P. Kämpf, Or. B. Kalbskopf, H.-G. Karrenberg, Oipl.-Phys. H. Keller-Rudek, Oipl.-Chem. C. Koeppel, R. Kalb, Or. M. Kotowski, E. Kranz, E. Krawczyk, Oipl.-Chem. I. Kreuzbichler, Or. W. Kurtz, M. Langer, Or. B. Ledüc, H. Mathis, E. Meinhard, M. Meßer, C. Metz, K. Meyer, E. Mlitzke, Dipl.-Chem. B. Mohsin, Or. U. Neu-Becker, K. Nöring, Oipl.-Min. U. Nohl, Dr. U. Ohms-Bredemann, Dr. H. Pscheidl, Dipl. Phys. H.-J. Richter-Oitten, E. Rudolph, Or. B. Sarbas, Or. R. Schemm, Dr. 0. Schiöberg, V. Schlicht, Oipl.-Chem. 0. Schneider, E. Schneider, A. Schwärzet, Or. B. Schwager, R. Simeone, Or. F. Stein, Or. C. Strametz, Dr. G. Swoboda, Dr. D. Tille, A. Tuttas, Dipl.-Phys. J. Wagner, R. Wagner, M. Walter, Or. E. Warkentin, Or. C. Weber, Or. A. Wietelmann, Dr. M. Winter, Or. B. Wöbke, K. Wolff GMELIN ONLINE Or. G. Olbrich Or. P. Kuhn Or. R. Baier, Or. K. Beesk, Or. B. Becker, Oipl.-Chem. E. Best, Or. H.-U. Böhmer, Oipl.-Phys. R. Bast, Dr. A. Brand!, Or. R. Braun, Or. T. Buck, H. Hanz, Oipl.-Phys. C. Heinrich-Sterze!, Or. S. Kalwellis-Mohn, Or. A. Kirchhoff, Or. M. Körfer, Oipl.-Chem. H. Köttelwesch, Or. V. Kruppa, Or. M. Kunz, Oipl.-Chem. R. Maass, Or. A. Nebel, Oipl.-Chem. R. Nohl, Or. M. Nahten, H. Rein hardt, Or. B. Rempter, Oipl.-Ing. H. Vanecek, Oipl.-Phys. M. Weiss Volumes published on "Sulfur" (Syst. No. 9) Sulfur A 1 - History (in German) - 1942 Sulfur A 2 - Occurrence. Technology of Sulfur and lts Compounds. Colloidal Sulfur. Toxicity (in German)- 1953 Sulfur A 3 - The Element. Preparation in Pure State. Properties (in German) - 1953 Sulfur B 1 - Hydrides and Oxides of Sulfur (in German) - 1953 Sulfur B 2 - Sulfur-Oxygen Acids (in German) - 1960 Sulfur B 3 - Compounds (concluded) (in German) - 1963 Sulfur-Nitrogen Compounds 1 - Compounds with Sulfur of Oxidation Number VI (in German) - 1977 Sulfur Suppl. Vol. 1 - Thionyl Halides (in German) - 1978 Sulfur Suppl. Vol. 2 - Sulfur Halides (in German) - 1978 Sulfur Suppl. Vol. 3 - Sulfur Oxides (in German) - 1980 Sulfur Suppl. Vol. 4a/b- Sultanes- 1983 Sulfur-Nitrogen Compounds 2 - Compounds with Sulfur of Oxidation Number IV - 1985 Sulfur-Nitrogen Compounds 3 - Compounds with Sulfur of Oxidation Number IV - 1987 Sulfur-Nitrogen Compounds 4 - Compounds with Sulfur of Oxidation Number IV - 1987 Sulfur-Nitrogen Compounds 5 - Compounds with Sulfur of Oxidation Number IV - 1990 Sulfur-Nitrogen Compounds 6 - Compounds with Sulfur of Oxidation Number IV - 1990 Sulfur-Nitrogen Compounds 7 - Compounds with Sulfur of Oxidation Number IV - 1991 Sulfur-Nitrogen Compounds 8 - Compounds with Sulfur of Oxidation Number IV - 1991 Sulfur-Nitrogen Compounds 9 - Compounds with Sulfur of Oxidation Number II - 1993 Sulfur-Nitrogen Compounds 10a- Compounds with Sulfur of Oxidation Number II- 1994 (present volume) Gmelin Handbock of lnorganic and Organemetallic Chemistry 8th Edition s Sulfur-Nitrogen Compounds Part 10a Compounds with Sulfur of Oxidation Number II With 14 illustrations AUTHORS Norbert Baumann, Hans-Jürgen Fachmann, ReimundJotter, Alfons Kubny EDITORS Norbert Baumann, Hans-Jürgen Fachmann, Reimund Jotter, Alfons Kubny NOMENCLATURE Ursula Hettwer CHIEF EDITOR Alfons Kubny System Number 9 Springer-Verlag Berlin Heidelberg GmbH 1994 LITERATURE CLOSING DATE: 1991 IN MANY CASES MORE RECENT DAT A HAVE BEEN CONSIDERED Library of Congress Catalog Card Number: Agr 25-1383 ISBN 978-3-662-06353-8 ISBN 978-3-662-06351-4 (eBook) DOI 10.1007/978-3-662-06351-4 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concemed, specifically those of translation, reprinting, reuse of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under § 54 of the German Copyright Law where copies are made for other than private use, a Iee is payable to "VerwertungsgeseUschaft Wort", Munich. © by Springer-Verlag Berlin Heidelberg 1994 Originally published by Springer-Verlag Berlin· Haideiberg · New York · London · Paris ·T okyo · Hong Kong ·Barcelona in 1994 Softcover reprint of the hardcover 8th edition 1994 The use of 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 proteelive laws and regulations and therefore free torgenerat use. Preface 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. The following chapter present a detailed survey of other 811-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=NNR2, R = organyl). Only the reac 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. The description of 811-N compounds with two-coordinate sulfur fills a large part of this volume. Thiohydroxylamines (HSNR2), thiooximes (HSN=R), and thionitrous acid (HSNO) are examples of this class of compounds. Next, sulfur amide halogenides (XSNH2, X= F, Cl) and their derivatives (amino-halogeno-sulfanes), including numerous examples of N,N-diorganyl substituted amino-halogeno-sulfanes (XSNR2, X= F, Cl, Br, I; R = organyl) and salts of the cation (XS) N+ (X=Cl, Br), are described. N,N-Diorganyl-substituted amino-chloro-sulfanes, 2 which can be obtained directly from secondary amines and SCl2, are important intermediates in syntheses. ClSNR is added to olefines and alkynes to give 1 ,2-addition products. Reactions 2 with secondary amines give diaminosulfanes. (ClS)zN+ is added to alkenes and alkynes to give sulfur-nitrogen compounds. The last sections deal with sulfur amide hydroxide derivatives (ROSNR2) and S-phospho rus-substituted thiohydroxylamines (R P(X)SNR2, X=O, S). Garnpounds of the type 2 (RO)zP(X)SNR2 (X=O, S) are effective as pesticides in the case of X=O and aceeierate the vulcanization of rubber in the case of X= S. The nomenclature used for acyclic sulfur(II)-nitrogen compounds follows current IUPAC recommendations and the practice in Chemical Abstracts. The Iiterature up to 1991 has been fully evaluated, and in many cases more recent publi cations are included. The series is continued with the description of sulfur diamide derivatives in the volume "Sulfur-Nitrogen Compounds", Part 10b, 1994. Frankfurt am Main Alfons Kubny November 1994 X Remarks on Abbreviations and Standards Physical data are cited in short form using abbreviations: measured density density calculated from X-ray data m.p. melting point; dec.: melting with decomposition b.p. boiling point, given in "C/Torr IR infrared spectrum. The medium of measurement (the physical state or a solvent) is given in parentheses. For the absorption maxima (Vibration frequencies v in cm-1), intensity and shape are abbreviated as usual: s (strong), vs (very strong), w (weak), vw (very weak), vvw (very very weak), m (medium), br (broad), sh (shoulder). The assigned bands are usually labeled with the symbols v for o y stretching, for in-plane bending, for out-of-plane bending, p for rocking, and -r for torsion vibration; the symbols s and as• e.g., in V5 and V85, mean symmetric and antisymmetric. Raman Raman spectrum. For abbreviations, see IR. uv ultraviolet spectrum. The medium of measurement is set in parentheses. The wavelength of the absorption maximum "-max is given in nm followed by the extinction coefficient E or log E, E in L . cm-1 . mol-1, in parentheses; sh means shoulder, br means broad. PES photoelectron spectroscopy X(U)PS X-ray (ultraviolet) photoelectron spectroscopy NMR nuclear magnetic resonance spectrum, noise decoupling is indicated by braces ( ). o Solvent and standard are given in parentheses. For (chemical shift in ppm) downfield shift is indicated by a positive sign as recommended by IUPAC. Stan dard substances (if not otherwise cited) are TMS (= Si(CH3)4) as internal standard for 1H and 13C NMR, neat CH3N02 as external standard for 14N NMR and 15N NMR, CFCl3 as internal standard for 19F NMR, and 85% H3P04 as external standard for 31P NMR. The multiplicity of the signal is given in parentheses: s (singlet), d (doublet), t (triplet), q (quartet), quint (quintet), sept (septet), m (multiplet). The assignment is given behind the multiplicity; if necessary for clarity the assigned atoms are underlined. "J (coupling constant in Hz) is fixed by the number of bonds involved n and the coupling nuclei (e.g., 1J(13C, H)), or by listing the coupling groups (e.g., 3J(CH2, CH3)) NQR nuclear quadrupole resonance spectrum ES(P)R electron spin (paramagnetic) resonance MS mass spectrum. m/e = mass/charge; M+ = molecular ion (1 +); relative intensity in parentheses EIMS electron impact mass spectrum FIMS field ionization mass spectrum CIMS chemical ionization mass spectrum Gmeliri Handbook S-N Comp. 10a