Darstellung von Tetramethylammoniumazidsulfit und Tetramethylammoniumcyanat‐Schwefeldioxid‐Addukt, [(CH3)4N]+[SO2N3]–, [(CH3)4N]+ [SO2OCN]– und Kristallstruktur von [(CH3)4N]+[SO2N3]–

Preparation of Tetramethylammonium Azidosulfite and Tetramethylammonium Cyanate Sulfur Dioxide‐Adduct, [(CH₃)₄N]⁺[SO₂N₃]^–, [(CH₃)₄N]⁺[SO₂OCN]^– and Crystal Structure of [(CH₃)₄N]⁺[SO₂N₃]^– Tetramethylammonium azide forms with sulfur dioxide an azidosulfite salt. It is characterized by NMR and vibrational spectroscopy and the crystal structure analysis. [(CH₃)₄N]⁺[SO₂N₃]^– crystallizes in the monoclinic space group P2₁/c with a = 551.3(1) pm, b = 1095.2(1) pm, c = 1465.0(1) pm, β = 100.63(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–N interaction between the N^3– anions and the SO₂ molecules. The S–N distance of 200.5(2) pm is longer than a covalent single S–N bond. The structure is compared with ab initio calculated data. Furthermore an adduct of tetrametylammonium cyanate and sulfur dioxide is reported. It is characterised by NMR and vibrational spectroscopy. The structure is calculated by ab initio methods.     

Synthesis of (CH3C(CH2PPh2)3)CoL complexes (L = O2CO,S2CO,O2SO) through metal-assisted CO2, CS2, SO2 oxidation. Crystal structure of (CH3C(CH2PPh2)3)CO(O2SO)

The solution obtained by reduction of [(triphos)CO(μ-Cl)₂Co(triphos)]⁺² (triphos = CH₃C(CH₂PPh₂)₃) with Na/Hg reacts with CO₂, CS₂ and SO₂ to give (triphos)Co(O₂CO), (triphos)Co(S₂CO), and (triphos)Co(O₂SO), respectively. The molecular structure of the last has been established by X-ray difraction.     

Methanesulfonamide in Superacids: Investigations of the CH3SO2NH3+ Cation

The preparation of protonated methanesulfonamide was carried out using the superacidic systems HF/AsF₅ and HF/SbF₅. The vibrational spectroscopic characterization was supported by quantum chemical calculations performed with the PBE1PBE method using the 6‐311G++(3df, 3pd) basis set. A remarkable long nitrogen–sulfur bond length of 1.804(6) Å was observed in a single‐crystal X‐ray structure analysis of [CH₃SO₂NH₃]⁺[Sb₂F₁₁]^–. It crystallizes in the orthorhombic space group P2₁/c with four formula units in the unit cell. Furthermore the crystal structure of CH₃SO₂NH₂ was revisited.     

Synthesis of sulphonated aminomethylphosphines and some nickel(II), palladium(II), platinum(II) and rhodium(I) complexes. Crystal structure of [Et3NH][(Ph2PCH2)2 N(CH2)2SO3]

Summary Aminoalkanesulphonic acids H₂N(CH₂) _n SO₃H, (n = 1, 2 or 3) react with phosphonium salts [R₂P(CH₂OH)₂]Cl (R = Ph or Cy, Cy = cyclohexyl) in the presence of Et₃N to give the sulphonated aminomethylphosphines [Et₃NH] [(R₂PCH₂)₂N(CH₂) _n SO₃] (R = Ph, n = 1, 2 or 3; R = Cy, n = 1). The single crystal X-ray structure of [Et₃NH] [(Ph₂PCH₂)₂N(CH₂)₂SO₃] has been determined. Some Ni^II, Pd^II, Pt^II and Rh^I complexes of the phosphines have been prepared.     

A temperature‐dependent kinetics study of the reaction of O(3PJ) with (CH3)2SO

A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics of the reaction of ground state oxygen atoms, O(³P_J), with (CH₃)₂SO (dimethylsulfoxide) as a function of temperature (266–383 K) and pressure (20–100 Torr N₂). The rate coefficient (k_R1) for the O(³P_J) + (CH₃)₂SO reaction is found to be independent of pressure and to increase with decreasing temperature. The following Arrhenius expression adequately describes the observed temperature dependence: k_R1(T) = (1.68 ± 0.76) × 10_?12 exp[(445 ± 141)/T] cm³ molecule^?1 s^?1, where the uncertainties in Arrhenius parameters are 2σ and represent precision only. The absolute accuracy of each measured rate coefficient is estimated to be ±30%, and is limited predominantly by the uncertainties in measured (CH₃)₂SO concentrations. The observed temperature and pressure dependencies suggest that, as in the case of O(³P_J) reactions with CH₃SH and (CH₃)₂S, reaction occurs by addition of O(³P_J) to the sulfur atom followed by rapid fragmentation of the energized adduct to products. The O(³P_J) + (CH₃)₂SO reaction is fast enough so that it could be a useful laboratory source of the CH₃SO₂ radical if this species is produced in significant yield. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 156–161, 2002; DOI 10.1002/kin.10040     

Hg2(CH3SO3)2: Synthese,Kristallstruktur, thermisches Verhalten und Schwingungsspektroskopie

Hg₂(CH₃SO₃)₂: Synthesis, Crystal Structure, Thermal Behavior, and Vibrational Spectroscopy Colorless single crystals of Hg₂(CH₃SO₃)₂ are formed in the reaction of HgO, Hg, and HSO₃CH₃. In the monoclinic compound (I2/a, Z = 4, a=883.2(2), b=854.0(2), c=1188.9(2) pm, β = 92.55(2)°, R_all=0.0445) the Hg₂²⁺ ion is coordinated by two monodentate CH₃SO₃^— anions. Further contacts Hg‐O occur in the range from 262 to 276 pm and lead to a linkage of the [Hg₂(CH₃SO₃)₂] units. The thermal analysis shows that Hg₂(CH₃SO₃)₂ decomposes at 300° yielding elemental mercury. The mass numbers of the species evolved lead to the assumtion that SO₃, SO₂, CO₂, CO and H₂CO are formed during the reaction. In the IR and the Raman spectrum the typical vibrations of the CH₃SO₃^— ion are observed, the Raman spectrum shows the Hg‐Hg stretching vibration at 177 cm^—1 within the Hg₂²⁺ ion additionally.     

Polysulfonylamine. XXXVII. Darstellung von Quecksilberdimesylamiden. Kristall- und Molekülstrukturen von Hg[N(SO2CH3)2]2, Hg[{N(SO2CH3)2}2(DMSO)2] und Hg[{N(SO2CH3)2}2(HMPA)]

Polysulfonyl Amines. XXXVII. Preparation of Mercury Dimesylamides. Crystal and Molecular Structures of Hg[N(SO₂CH₃)₂]₂, Hg[{N(SO₂CH₃)₂}₂(DMSO)₂], and Hg[{N(SO₂CH₃)₂}₂(HMPA)] Hg[N(SO₂CH₃)₂]₂ ( 1 ) and Hg₂[N(SO₂CH₃)₂]₂ ( 2 a ) are formed as colourless, sparingly soluble precipitates when solutions of Hg(NO₃)₂ or Hg₂(NO₃)₂ in dilute nitric acid are added to an aqueous HN(SO₂CH₃)₂ solution. By a similar reaction, Hg₂[N(SO₂C₆H₄ ? Cl? 4)₂]₂ is obtained. 1 forms isolable complexes of composition Hg[N(SO₂CH₃)₂]₂ · 2 L with L = dimethyl sulfoxide (complex 3 a ), acetonitrile, dimethyl formamide, pyridine or 1,10-phenanthroline and a (1/1) complex Hg[N(SO₂CH₃)₂]₂ · HMPA ( 4 ) with hexamethyl phosphoramide. Attempted complexation of 2 a with some of these ligands induced formation of Hg⁰ and the corresponding Hg^II complexes. Crystallographic data (at -95°C) are for 1: space group 14₁/a, a = 990.7(2), c = 2897.7(8) pm, V = 2.844 nm³, Z = 8, D_x = 2.545Mgm^?3; for 4a: space group P1 , a = 767.8(2), b = 859.2(2), c = 925.2(2)pm α = 68.44(2), β = 86.68(2), γ = 76.24(2)°, V = 0.551nm³, Z = 1, D_x = 2.113 Mgm^?3; for 4: space group P2₁/c, a = 1041.3(3), b = 1545.4(3), c = 1542.5(3) pm, β = 100.30(2)°, V = 2.474nm³, Z = 4, D_x = 1.944Mgm³. The three compounds form molecular crystals. The molecular structures contain a linear or approximately linear, covalent NHgN moiety; the Hg? N distances and N? Hg? N angles are 206.7(4) pm and 176.3(2)° for 1, 207.2(2) pm and 180.0° for 3a, 205.7(4)/206.7(4) pm and 170.5(1)° for 4. In the complexes 3a and 4, the 0-ligands are bonded to the Hg atoms perpendicularly to the N? Hg? N axes, leading in 3a to a square-planar trans-(N₂O₂) coordination with Hg? 0 261.2(2) pm and N? Hg? O 92.3(1)/87.7(1)°, in 4 to a slightly distorted T-shaped (N₂O) geometry with Hg? 0 246.2(4)pm and N? Hg? 0 96.7(1)/92.0(1)°. In all three structures, the primary coordination is extended to a severely distorted (N₂O₄) hexacoordination by the appropriate number of secondary, inter- and/or intramolecular Hg…?0 inter-actions (0 atoms from sulfonyl groups, Hg…?O distances in the range 280—300pm). The intramolecular Hg…?O interactions give rise to nearly planar four-membered [HgNSO] rings. The molecule of 1 has a two-fold axis through the bisector of the N? Hg? N angle, the molecule of 3a an inversion center at the Hg atom. The molecule of 4 has no symmetry.     

Darstellung und Kristallstruktur des TetramethylammoniumthiocyanatSchwefeldioxid‐Adduktes, (CH3)4N+SCN– · SO2

Preparation and Crystal Structure of the Tetramethylammonium Thiocyanate Sulfur Dioxide Adduct, (CH₃)₄N⁺SCN^– · SO₂ Tetramethylammonium thiocyanate reacts with sulfur dioxide under formation of tetramethylammonium thiocyanate sulfur dioxide adduct. The resulting salt is characterised by NMR and vibrational spectroscopy and its crystal structure. (CH₃)₄N⁺SCN^– · SO₂ crystallizes in the monoclinic space group P2₁/c with a = 578.4(1) pm, b = 1634.3(1) pm, c = 1054.6(1) pm, β = 105.17(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–S interaction between the NCS^– anion and the SO₂ molecule. The NCS–SO₂ distance of 301.02(9) pm is longer than a covalent single bond, thus the compound is rather described as an adduct. The structure is compared with ab initio calculated data.     

Synthesis and Crystal Structure of Hexakis(N—allylthiourea)tetracopper(I) Tetratrifluoromethanesulfonate, [Cu4{CH2=CHCH2NHC(S)NH2}6](SO3CF3)4

Hexakis(N—allylthiourea)tetracopper(I) Tetratrifluoromethanesulfonate, [Cu₄{CH₂=CHCH₂NHC(S)NH₂}₆](CF₃SO₃)₄ (sp.gr.P2₁/n, a = 13.5463(8), b = 24.129(2), c = 19.128(1)Å, β = 108.053(6)°, Z = 4, R = 0.0440 for 13548 unique reflections) was obtained by reduction of Cu(CF₃SO₃)₂ with excess of N—allylthiocarbamide in benzene medium. Four crystallographical independent Cu atoms possess trigonal environment of three S atoms of CH₂=CHCH₂NHC(S)NH₂ moiety and form Cu₄S₆⁴⁺ adamantane—like fragments. The latteres are connected with CF₃SO₃^— anions via (C)—H···F hydrogen bonds.     

Analyse conformationnelle théorique du diméthylsulfoxyde (CH3)2SO

Résumé La méthode SCF-LCAO-MO dans l'approximation CNDO/2 est utilisée pour l'étude de l'analyse conformationnelle du diméthylsulfoxyde (CH₃)₂SO. On montre ainsi que, parmi les déterminations géométriques de la littérature, celle (r _OIV) obtenue par Dreizler et Coll. en 1969 au moyen de la spectroscopie de microondes semble devoir être retenue. La carte de potentiel, décrivant la rotation simultanée des deux groupements méthyle autour des liaisons (S-C), est tracée: elle montre que la molécule (CH₃)₂SO appartient bien au groupe de symétrie C _s, non seulement au niveau des atomes lourds (C, S, O) mais aussi à celui des hydrogènes. On note toutefois que les deux hydrogènes qui, dans la conformation (60, 60), auraient été dans le plan CSC, sont alors décalés tous deux de quelque 3,64° hors de ce plan et du côté de l'atome d'oxygène. La barrière à la rotation d'un CH₃ est trouvée égale à 3,5 kcal/mole (expérimentalement: 2,8 kcal/mole [7]). Un découpage bicentrique de l'énergie totale montre enfin que 60% des variations de cette grandeur sont dûs à la seule somme, E (S...H) des interactions dans l'espace entre l'atome de soufre et les six atomes d'hydrogène.

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Theoretical conformational analysis of dimethylsulfoxide (CH₃)₂SO

The conformational analysis of (CH₃)₂SO is investigated within the framework of the CNDO/2 approximation. The preferred conformation of heavy atoms (C, S, O) is found to be the one (r _OIV) which was proposed by Dreizler et al. in 1969 on the basis of microwave measurements. The map of isoenergy curves was drawn, describing the variation of energy as a result of mutual rotation of the two methyl groups. This showed that the equilibrium symmetry for the complete molecule, including the hydrogens, was C _sHowever, it may be noticed that the two hydrogens which, for the (60, 60) conformation, would have been located into the CSC plane, are actually staggered of 3.64° out of this plane and nearer to the oxygen atom than to the sulphur lone pair. The rotational barrier for one CH₃ group is 3.5 kcal/mole, in agreement with the experimental value (2.8 kcal/mole [7]). A bicentric energy partitioning shows that about 60% of the variation in total energy is reflected by the single sum, E(S...H), of the spatial interaction terms between sulphur and the six hydrogens.

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Zusammenfassung Die Konformation von (CH₃)₂SO wird im Rahmen des CNDO/2-Verfahrens analysiert, wobei sich für C-, S- und O-Atome das gleiche Ergebnis wie bei Mikrowellenmessungen (Dreizler, 1969) ergibt. Ferner wird die Energiehyperfläche für Methyl-Rotationen angegeben, mit der Symmetrie C _sam tiefsten Punkt. Allerdings sind die zwei H-Atome, die bei der (60, 60)-Konformation in der CSC-Ebene liegen sollten, um 3,64° aus dieser Ebene herausgedreht und näher an den einsamen Elektronen des Sauerstoffs als an denen des Schwefels. Die Rotationsbarriere einer CH₃-Gruppe beträgt 3,5 kcal/ Mol (experimentell 2,8 kcal/Mol [7]). Eine Energieaufspaltung auf Zentrenpaare zeigt, daß etwa 60% der Änderung der Gesamtenergie in der Einfachsumme E(S...H) der räumlichen Wechselwirkungs-systeme zwischen den S- und den sechs H-Atomen enthalten ist.

     

CH3SOx (x＝0, 1)与三线态Oy (y＝1, 2, 3)反应机理的理论研究

采用B3LYP方法和6-311G(d, p)基组对CH₃S及其氧化后继物CH₃SO与O_y (y＝1, 2, 3)反应形成酸雨的微观机理进行了理论研究. 对反应势能面上的各驻点进行几何构型全优化. 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系. 找到了7条生成SO₂的反应途径, 其中CH₃S与O直接反应得到产物CH₃和SO最容易进行; CH₃S先与O₃反应, 其产物再与O₃反应得到CH₃SO₂, CH₃SO₂最后分解得到CH₃S和SO₂较容易进行, 其它的反应较难进行.     

Synthesis,Crystal Structure,and Spectroscopic Characterization of the Borazine Derivatives [B{CH2(SiCl3)}NH]3 and [B{CH2(SiCl2CH3)}NH]3

The borazine derivatives B, B′, B″‐tris[(trichlorosilyl)methyl]borazine [B{CH₂(SiCl₃)}NH]₃ ( 1 ), and B, B′, B″‐tris[{dichloro(methyl)silyl}methyl]borazine [B{CH₂(SiCl₂CH₃)}NH]₃ ( 2 ) were prepared by reacting (Cl₃Si)CH₂(BCl₂) ( 3 ) and [Cl₂(CH₃)Si]CH₂(BCl₂) ( 4 ) with hexamethyldisilazane (hmds), respectively. Both compounds, 1 and 2 crystallize in space group R3c with a = 1712.53(4), c = 1230.33(4) pm, Z = 6, R₁ = 0.030, and a = 1713.8(2), c = 1258.7(2) pm, Z = 6, R₁ = 0.034, respectively. According to the single crystal X‐ray diffraction analyses, the title compounds show a planar B₃N₃ six‐membered ring with B—N distances of 142.3(3) pm (point symmetry C₃) and synfacial oriented substituents. The borazine derivatives have also been characterized by NMR and IR spectroscopy as well as by MS spectrometry.     

Schwingungsspektren und Kraftkonstanten von Cl3SiP(CH3)2 und Cl3SiAs(CH3)2

Vibrational Spectra and Force Constants of Cl₃SiP(CH₃)₂ and Cl₃SiAs (CH₃)₂ The i.r. and Raman spectra of Cl₃SiP(CH₃)₂ and Cl₃SiAs (CH₃)₂ have been recorded and assigned. A normal coordinate analysis has been made using a modified valence force field. The SiP force constant is slightly higher than those of alkylsilylphosphines, whereas a similar effect is not found for the SiAs bond.     

Darstellung von Dimethyl-N-Chlorammoniumtrifluormethansulfonat ((CH3)2NClH+ CF3SO3−)

Synthesis of Dimethyl-N-Chloroammonium Trifluoromethane Sulfonate ((CH₃)₂NClH⁺ CF₃SO₃^?) The weak base dimethyl-N-chloroamine, (CH₃)₂NCl, reacts with trifluormethane sulfonic acid at ?40 to ?30°C to give dimethyl-N-chloroammonium trifluoromethane sulfonate (CH₃)₂NClH⁺CF₃SO₃^?. The extremely hygroscopic salt decomposes upon melting at 107 to 108°C and thus is slightly more stable than the hydrogensulfate. Water or methanole liberate dimethyl-N-chloroamine from the salt. The salt is insoluble in ether and decomposes after dissolving in methylene chloride to give dimethylammonium trifluoromethane sulfonate (CH₃)₂NH₂⁺CF₃SO₃^?.     

Spektroskopische Untersuchungen an Schwefelverbindungen. IV. Darstellung,Infrarot- und Raman-Spektren von Derivaten des CH3SO2NH2 und (CH3SO2)2NH

The compounds I—XIV (see above) were prepared, in part for the first time, and investigated by infrared and Raman spectroscopy. The group vibrations of the CH₃SO₂N fragment occur in remarkably narrow regions which facilitate the rather complete assignment of the observed frequencies.     

Schwingungsspektren und Kraftkonstanten der Übergangsreihen OP(N(CH3)2)3 – OP(CH3)3 und SP(N(CH3)2)3 – SP(CH3)3

Vibrational Spectra and Force Constants of the Series OP(N(CH₃)₂)₃ – OP(CH₃)₃ and SP(N(CH₃)₂)₃ – SP(CH₃)₃ The vibrational spectra (IR and Raman) of the compounds of the title series are recorded and assigned to the normal vibrations. By a simplified force field the valence force constants are calculated and discussed. The results are compared with those of the NMR spectroscopy.     

Synthese,Spektren und Strukturen einfacher Derivate des Tris(bis(trimethylsilyl)methyl)indiums,In(CH(Si(CH3)3)2)3

Syntheses, Spectra, and Structures of Simple Derivatives of Tris(bis(trimethylsilyl)methyl Indium, In(CH(Si(CH₃)₃)₂)₃ Like trimethyl- or triethylindium tris(disyl)indium, In(CH(SiMe₃)₂)₃ (≙ InR₃) also reacts with equimolar amounts of water, D₂O, MeOH, HCl and HCOOH, respectively, in ether solution at room temperature to form the corresponding alkane, here (Me₃Si)₂CH₂, and the simple monosubstitution products R₂InX. With the dibasic oxalic and sulfuric acid the multinuclear derivatives (R₂In)₂C₂O₄ and [RIn(R₂In)₂(SO₄)₂]₂ are formed, respectively. The halogenides R₂InCl, RInCl₂, and RInBr₂ have been prepared by metathesis from InHal₃ and InR₃ (molar ratios 1 : 2 and 2 : 1). The ¹H, ¹³C, and ²⁹Si NMR- as well as the vibrational spectra (IR, Raman) are discussed. According to the X-ray structure elucidations the monosubstitution products R₂InX (with X = OH, OMe, Cl) are dimeric in the solid state and consist of planar, centrosymmetric fourmembered In₂X₂ skeletons. The dibromide RInBr₂ forms a polymeric chain structure with five-fold co-ordinated metal centres and vertex linked, alternately appearing planar as well as slightly folded In₂Br₂-moities. The “sesquisulfate” [R₅In₃(SO₄)₂]₂ has an uncommon, cage-like structure with four as well as five-fold co-ordinated In atoms. The structural data could not be optimally refined due to the highly disordered disyl groups.     

Reaktionen von Trimethylstiban in den supersauren Systemen XF/MF5 (X = H,D; M = As,Sb), Kristallstrukturen von (CH3)3SbD+SbF6– und (CH3)3SbSb(CH3)32+(SbF6–)2 · SO2

Reactions of Trimethylstibine in the Superacidic Systems XF/MF₅ (X = H, D; M = As, Sb), Crystal Structures of (CH₃)₃SbD⁺SbF₆^– and (CH₃)₃SbSb(CH₃)₃²⁺(SbF₆^–)₂ · SO₂ The reaction of trimethylstibine in the superacidic systems XF/MF₅ (M = As, Sb; X = H, D) leads to the trimethylstibonium hexafluorometallates. The resulting salts are characterised by vibrational spectroscopy and their crystal structures. Decomposition of trimethylstibonium hexafluoroantimonate in sulphur dioxide at room temperature ends in the formation of hexamethyldistibonium bis(hexafluoroantimonate) as a sulphur dioxide adduct, verified by its crystal structure and vibrational spectra.     

The [Au(CH3SO3)4]– Anion in the Crystal Structures of M[Au(CH3SO3)4] (M = Li,Na, Rb)

The reactions of Au(OH)₃, M₂CO₃ (M = Li, Na, Rb), and methanesulfonic acid at elevated temperatures in sealed glass ampoules lead to single crystals of M[Au(CH₃SO₃)₄] (M = Li, Na, Rb). In the crystal structures of Li[Au(CH₃SO₃)₄] (tetragonal, I$\bar{4}$ , Z = 2,a = 938.64(2) pm, c = 917.01(3) pm, V = 807.93(4) ų) and Rb[Au(CH₃SO₃)₄] (tetragonal, P$\bar{4}$ 2₁c, Z = 2, a = 946.7(1) pm,c = 889.9(1) pm, V = 797.6(2) ų) the complex aurate anions are linked by the M⁺ ions in three dimensions. Contrastingly, in the structure of Na[Au(CH₃SO₃)₄] (triclinic, P$\bar{4}$ , Z = 1, a = 540.04(2) pm,b = 863.75(2) pm, c = 973.29(3) pm, α = 72.694(2)°, β = 75.605(2)°, γ = 77.687(2)°, V = 415.05(2) ų) the complex anions are connected into layers that are further connected by weak hydrogen bonds. The thermal decomposition of Li[Au(CH₃SO₃)₄] was monitored up to 500 °C and leads in a multi‐step process to elemental gold and Li₂SO₄.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [O3SS(NPPh3)2] · CH3CN, [SO(NPPh3)2] und [SCl(NPMe3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Syntheses and Crystal Structures of [O₃SS(NPPh₃)₂] · CH₃CN, [SO(NPPh₃)₂], and [SCl(NPMe₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SO₂ and SOCl₂, respectively, and by the reaction of Me₃SiNPMe₃ with S₂Cl₂. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O₃SS((NPPh₃)₂)] · CH₃CN : Space group Pca2₁, Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at ?60°C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S? S bond length of 218.2 pm and bond lengths S? N of 161.2 and P? N of 160.1 pm. [SO(NPPh₃)₂] : Space group P2₁/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at ?50°C: a = 1173.1, b = 1585.6, c = 1619.2 pm, b? = 98.13°. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S? N 166 pm and P? N 163 pm in average. [SCl(NPMe₃)₂]Cl : Space group P1 , Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 613.2, b = 1030.3, c = 1111.4 pm, α = 88.48°, b? = 88.01°, γ = 83.10°. The compound forms ions [SCl(NPMe₃)₂]⁺ and Cl^?. In the cation the sulfur atom is ?-tetrahedrally coordinated with a long S? Cl distance of 246.9 pm and bond lengths S? N of 155.3 pm and P? N of 164.3 pm in average.