JUL

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NATURFORSCHUNG Teil b

Anorganische Chemie, Organische Chemie

Kuratoriu.m Sohriftfiihrende Herausgeber

H. P. FRrrz, Miinohen E. BttNNING, Tiibingen A. BUTEN.ANDT, Miinohen M. EIGEN, Gottingen

EL NoTH, Miinohen J;t. GoM!'PER, Miinohen

W. GENTNER, Heidelberg W. HEISENBERG, Miinohen

BAND 3Ib

Beratende Herausgeber

E. 0. FrsOHER, Miinohen G. GtrEMANN, Regensburg D. SOHULTE-FROHLINDE, Miilheim/R. F. F. SEELIG, Tiibingen W. STEGLIOH, Bonn A. WEISS, Miinohen

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Atomic Transport in Solids and Liquids Proceedings of the Europhysics Conference, held at Marstrand, Sweden, 1970.

Editors: A. Lodding and T. Lagerwall, Chalmers University of Technology, Gothenburg.

Scientific Committee= Y. Adda, Centre d'Etudes Nuclliaires, Saclay V. B. Fiks, Semiconductor Institute, USSR Academy of Sciences, Leningrad Th. Heumann, Westfalische Wilhelms-Universitat, Munster H. B. Huntington, Rensselaer Polytechnic Institute, Troy, N.Y. A. Klemm, Max-Planck-lnstitut fur Chemie (Otto-Hahn-lnstitut), Mainz D. Lazarus, University of Illinois, Urbana, Ill. A. D. LeClaire, Atomic Energy Research Establishment, Harwell R. A. Swalin, University of Minnesota, Minneapolis H. Wever, Technische Universitat, Berlin

Contributing Participants: P. Adam B. Cleaver E. A. Aitken R. M. Cotts W. B. Alexander J. L. Crolet A. R. Alfnatt N. V. Doan T. R. Anthony K. Dreyer B. Baranowski J. Dupuy L. W. Barr V. B. Fiks D. K. Belashchenko C. P. Flynn F. Beniere R. J. Friauf M. Beyeler G. Frohberg D. Blackburn M. Gerl R. S. Bradley H. M. Gilder

D. G'rimme Th. 'Hehenkamp D. Heitkamp Ch. Herzig R. V. Hesketh P. S. Ho R. E. Hummel H. B. Huntington A. Klemm J. J. Kovenskij G. J. Kruger H. Kuper

A. Kvist D. Lazarus A. D. LeClaire A. B. Lidiard A. Lodding A. Lundlin J. R. Manning N. H. March H. Mehrer J. G. Mullen I. Okada A. Ott

D. T. Peterson N. L. Peterson R. Rosenberg S. J. Rothman A. Sawatzky J. N. Sherwood L. M. Slifkin A. M. Stoneham R. A. Swalin P. Thernquist I. M. Torrens H. J. V. Tyrrell

The book, containing 60 invited contributions from international first rank specialists, gives a comprehensive "state of science" review of the field and outlines the present trends of theory and experiment as well as technological applications. The most modern aspects of atomic mobility in metals, semi-conductors and ionic media are discussed with the aim to unite the physical and themical approaches and to coordinate the advanced research in different countries.

Special attention is given to the behaviour of thermally activated atoms subjected to electrical, thermodynamical and mechanical forces; atom transport under varying pressures; mobility models of liquids, thin films, surfaces and extended defects; isotope effects and ion conduction as means of identifying defect mechanisms.

434 pages (20x26 cm). Price: DM 120.-

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Contents z. Naturforsch, Vol. 81 b, No. 5, May 1976

.~. Original Communications

Oxofluoro-oxalato-vanadates(IV): Vibrational Spectrum and Crystal Structure of Naa[VOF(C204)2] · 6 H20 (In German) .. ,, H. RIESKAMP and R. MATTES 537 Oxotetrafluoro-vanadates(V): Crystal Structure of [enH2][VOF4(H20)]2 (In German)

... H. RIESKAMP and R. MATTES 541 Tetre.alkylammoniumpolyvanadates (In German) ... J. FucHs, S. MAHJOUR, and R. PALM 544 Contributions to the Study of Inorganic Non-Stoichiometric Compounds, V. Preparation and Electron Optical Investigation of FeNb11020, FeNb29074 and TiNb14037 (In German)

... H. BRUNNER, R. GRUEHN, and W. MERTIN 549 Crystal Structure and Vibrational Spectrum of Tetraamminegold(IIll-Nitrate (In German)

... M. WEISHAUPT and J. STRAHLE 554 Contributions to the Chemistry of Phosphorus, 62. About the Question of a1p N.MR pe tr sqopio Detection of Monomeric and Dimeric Phenyl Phosphorus a.nd the Ring Size of rganyl iyoloph.o.aphllolles (In German) ... M. BAUDLER, B. CARLSOHN, w. BOHM and o. °REUBOHlllNBAOH 558 Characterization of Tetrakis(isonitrile )platinum(Il)-tetrachloroplatinates(II), [Pt( CNR )4][PtCl4]

... H.J. KELLER and R. LORENTZ 565 Discussion of Chemical Equilibria (In German) ... TH. DUBLER, C. MAISSEN, and G. CALZAFERRI 569 Gamma Radiolysis of Aerated Aqueous Solution of Cytosine, III. Identification of Two New Radiolysis Products: l-Carbamoyl-5-hydroxyhydantoin a.nd N-Formylbiuret ... M. PoLVERELLI and R. TEoULE 580 On Labelled Compounds, XXVI. The 1,2,3-Trichloropropenylium Ion as Intermediate on the Fluorina-tion of 1,2,3,3-Tetrachloro-l-propene (In German) ... F. BOBERG and R. Voss 583 Synthesis and Photolysis of 5-Diazo-5-[lBC]-homoadamantan-4-one (In German) ... K.-P. ZELLER 586 Reactions with 2-Carboxyindole-3-acetic Aoid!mid s, 1• pru·o. i tl f ome lmides, their Condensations with Aromatic Aldehydes and Nitroso Compow1ds and j;J,1 il• 01,1pling with Diazonium Salts

... M. I. ALI, A. A. EL-SAYED, A. M. ABDEL-FATTAH, and A. M. EL-REEDY 589 The Reactivity of the C=N-Double Bond System, VIII. PMR-spectroscopic Studies on the E/Z-Isomerism of Alkyl a-Nitrocinnamates (In German) ... 0. S. WoLFBEIS 594 2 H-Pyrrolenine-N-oxide and N-Hydroxy-pyrrole (In German) ... R. KREHER and H. PAWELCZYK 599 Dissociation Constants of Some Hydroxamic Acids ... Y. K. AGRAWAL 605 Sesquiterpene Esters of Type A from Euonymus europaeua L. (In German)

... A. ROMER, H. THOMAS, and H. BuDZIKIEWIOZ 607

Bericbt

Recent Investigations on Cyclic Sulfur-Nitrogen-Halogen Compounds ... 0. GLEMSER 610 Inorganic Fivemembered Ring Systems Basing upon Silicon, Nitrogen and "Hetero Elements" (In German) ... U. WANNAGAT, M. ScHLINGMANN, and H. AUTZEN 621 The Reactions of Halogenocyclophosphazenes wit h Nitrogenous Bases ... R . A. SHAW 641 Phosphorus Compounds with the VI B Group Elements ... Y. MONTEIL and H. VINCENT 668 Synthesis of N ew Heterocycles by Halogenation of Tetrasulfur Tetranitride S4N4

... Y. MoNTEIL and H. VINCENT 673 Bonding in Cyclophosphazenes: Quantum and Experimental Support for DEWAR's Island Model

... J.-P. FAUCHER, J.-F. LABARRE, and R. A. SHAW 677 Preparation and Reactions of Sulfur-Nitrogen Ring Systems ... H. W. RoESKY 680

Notes

LiPbMIIIF6-Compounds and Pba(AIF6)2 and Pba(TiFa)2 (In German) ... J. GAILE and W. RfrDORFF 684 The Crystal Structure of Dy2Sea (In German) . . . K.-J. RANGE and R. LEEB 685 Structural Studies on Polyvalent Compounds of Iodine

.. . K. PROUT, N. M. STEVENS, A. CODA, V. TAZZOLI, R. A. SHAW, a.nd T. DEMIR 687 Monomeric Methyl Metal Diacetamido Complexes of Gallium and Antimony (In German)

... B. EBERWEIN, F. SILLE, and J. WEIDLEIN 689 The Preparation of Ha[Mn(CN)5NO] and Ha[Cr(CN)5NO] and their Ammonium Salts (In German)

.. . B. MOHAI and A. HORVATH 692 The Reaction of Endiols with Halogendisilanes (In German) . . . E. HENGGE and E. BRANDSTATTER 694 Berichtigungen 696

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Preparation and Reactions of Sulfur-Nitrogen Ring Systems*

HERBERT W. RoESKY Anorganisch-chemisches Institut der Universitat Frankfurt

(Z. Naturforsch. 31 b, 680-683 [1076]; received August 12, 1975)

X-ray, Sulfur-nitrogen Ring Systems, Silicon

Two routes for the preparation of (CHs)2SnS2N2 are given, which are kinetically controlled reactions. The molecule (CH3)2SnS2N2 was characterized by X-ray analysis. It is an interesting starting material for the preparation of S2N2CO and SsN20. The latter reacts with iminosulfur oxides and isocyanates under the formation of SsNsS02F and SsNsS02CF3. The structure of SsNsS02F was established by X-ray analysis. The bonding properties are discussed.

The cleavage of thin-nitrogen derivatives with SsN2Ch yields also five membered sulfur-nitrogen rings. The structure and properties of PsNsF5NSsN2 and CsNsF2NSsN2 are re-ported. Six, eight and ten membered rings are formed by the reactions of

(CHs)sSi-N =S=N-Si(CHs)s with FS02-N=S=O, these are S4N402 and S5N5+S3N304-, respectively. The cation S5N5+ is a planar molecule, while the oxygen containing species are puckered. In S4N402 the oxygens are attached to one sulfur atom, which has a tetrahedral configuration.

The structure of the silicon containing cyclic and bicyclic rings (CHs)2Si(NSN)2Si(CHs)2 and CHsSi(NSN)aSiCHs were determined.

Although tetrasulfur tetranitride was prepared 140 years ago, little is known about other kinetically controlled reactions in this field 1 . The preferred method for preparing S4N 4 is the reaction of sulfur chlorides having a composition "SCla" with am-monia. SCb is not known and therefore SCl2 is treated in carbon tetrachloride solution with chlorine.

4 SCl3 + 16 NH 3 - S 4 N4 + 12 NH4CI

Recently we used tin substitued amines instead of ammonia because the N-H (391 kJ mol-1 ) bond energy is significantly greater than the tin-nitrogen bond energy (e.g. in (CHs)sSnN(CH3)2167 kJ mol-1 ). Thus, other cyclic derivatives should be easy available from the reaction of tin-nitrogen com-pounds with inorganic halides. It should be added that in addition the formation of a tin-halogen bond is favoured 2.

* Paper, presented at the 1. International Symposium on Inorganic Heterocycles, Besanr;on (Franco), June 16--19, 1975.

Requests for reprints should be sent to Prof. Dr. H. W. RoESKY, Anorganisch-chemisches Institut Ider Universitat, Niederurseler Hang, D-6000 Frankfurt a . .M.

./""N I

2 s,c1, + 2 N[Sn(CH,),l, - i ;' + (CH,),sn + 4(CH,),SnCI +2S CH"Sn

CH/' " N

By using N[Sn(CHa)a]a as a nucleophile, it is also possible to get to the same product according to the following equations 3, 4.

(CH,)3Sn -N =S=N-Sn(CH,), + S -

The intermediates, sulfur and the tin substituted imlfur diimide, (CH3)3Sn-N =S=N-Sn(CH3)3, might be obtained before heating the reaction mixture. The structure of the cyclic tin compound (CHs)2SnS~N2 has been determined5, the molecule exifltcd of one four-membered and two five-mem-bered rings and the coordination number at the tin is five as shown below. The molecule has C1 symmetry.

MICRON Ex.1063 p.5

JI. W. ROESKY · PREPARATION AND REACTIONS OF SULFUR-NITROGEN RING SYSTEMS 681

The molecule is also a dimer in solution but monomeric in the gas phase. Another interesting feature of the structure is, that the molecule has nearly a planar form in the solid state. All the S-N bonds are of different length, the N-S-N and S-N-S bond angles being 116.8° and 118.1 °, respectively. The bond lengths are intermediate between that xp0ctod for a singl (l.74 ) and a double b nd

(1.54 )- ompariJlg t h n N angle of 1 3.2° with lilio N+ augle f ll6. 0 a ignifion.nLly 1liffcrono is obs 1·v cl, whi h is cansed b dil~ rent I T n d nsit.y. This ill.u.st.mtcs that it is to som

ext0)1L jnstifi cl t a:sign a formul oxitl.aU n number of + 2 for the sulfur bonded to tin and a formal oxidation number of + 4 for the sulfur atom located between the two nitrogen atoms. Recent work has shown that COF2 6 or SOF2 7 react at room tem-perature with the tin compound under insertion and elimination of dimethyltindifluoride.

+ COF2 - + (CH3)2SnF,

+ SOF, - .. () . (cH,),SnF, 'rh oyoli ke one is th frr t i· pr sentativ f a,

new •lass f ompow1ds that have b · ·omo readil A. Oes.

682 H. W. ROESKY · PREPARATION AND REACTIONS OF SULFUR-NITROGEN RING SYSTEM:s

By using the well-known compound SaN2Cb as a starting material and nitrogen-tin derivatives we were able to isolate bicyclic compounds 9, 10.

The question however, whether isomer 1 or 2 is formed has been established by X-ray analysis 11. It is found that the formation of the five-membered ring is favoured. By comparing the data of the SaN2Cl+ cation 12 with the N-SaN2 part of PaNaFsNSaN2 we observe that,

the S-S distance is considerably longer 2.200 A than in the cation 2.136 A. The electron density is apparently much higher. A further point of interest is, that the 6 :n:-electron S2N 2 part is not substantially influenced. It was confirmed by calculations on SaN2Cl+ that the ring may formally be regarded as a pseudo-aromatic 6:n:-electron system1a. Many compounds with S-N bonds may, of course, be synthesized from silicon-nitrogen derivatives. Typi-cal of these is (CHa)aSi-N =S=N-Si(CHs)a. On reac-tion with CHaSiCla and the corresponding tin deriva-tive the bicyclic silicon-sulfur-nitrogen compound is formed 14.

The molecule has exact D3-symmetrys. A related compound is obtained by using (CH3)2SiCb 1s. The eight-membered ring was confirmed by X-ray analysis 16• Both compounds are sensitive to moisture but can be sublimed without reduced pressure.

The products shown in the figures below resulted from the reaction of (CHa)3Si-N =S=N-Si(CHa)s with FS02-N=S=O in methylenechloride17.

MICRON Ex.1063 p.7

g, W, ROESKY · PREPARATION AND REACTIONS OF SULFUR-NITROGEN RING SYSTEMS 683

The ionic species can be formally regarded as being formed according to the following equation:

The ionic compound crystallizes with a mono-clinic cell, space group P21/c and four units of SsNs+SsNs04- per cell. The shape of the SsNs+ cation observed, differs greatly from the heart-shaped ion reported for S5N 5 + Al014- 18.

l H. W. RoESI