S Sulfur-Nitrogen Compounds: Part 10a: Compounds with Sulfur of Oxidation Number II

347 Pages·1994·8.6 MB·English

by  Norbert Baumann

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