Jürgen Schimkowiak

Cyclo-octasulphur as a ligand; preparation and X-ray crystal structure of [Ag(S8)2]AsF6

Reaction of AgAsF6 with S8 in liquid sulphur dioxide leads to [Ag(S8)2]AsF6, which contains cyclo-octasulphur ligands; the X-ray structure shows that the silver atoms achive distorted four-co-ordination by 1,3-linkages to two S8 rings.

X-Ray crystal structure of bis(1-oxo-1λ4,2,4λ4,3,5-trithiadiazole)silver hexafluoroarsenate(V); an unusual mode of co-ordination

Ag+ and S3N2O form a 1 : 2 complex; X-ray crystal structure of the As F6– salt shows linear co-ordination of Ag by the ring N atoms, with more distant O and F completing an octahedron.

How do silver(I) cations react with hydrogen cyanide? The crystal structure of [Ag(NCH)2][SbF6]

The reaction between Ag+ and HCN in liquid sulphur dioxide leads to the linear silver(I) complex [Ag(NCH)2]+, isolated as its [SbF6]– salt.

Darstellung und Eigenschaften von Cyclo-1λ6-metalla-3,5-ditha-2,4,6-triazenen / Synthesis and Properties of Cyclo-1λ6-metalla-3,5-dithia-2,4,6-triazenes

The metallacycles [Cl3MS2N3]2 (M = Mo, W) 1a and 2a have been obtained from reactions of S4N4 with Mo2Cl10 and WCl6, respectively, and from S3N3Cl3 with the hexacarbonyls M(CO)6. The adducts Cl3MS2N3 · CH3CN 1b and 2b are formed with acetonitrile, and the salts [Ph4As+][Cl4MS2N3-] 1c and 2c with addition of Ph4AsCl. Reactions of Mo2Cl10 and WCl6, respectively, with related S -N com pounds lead predominantly to 1a and 2a; Mo2Cl10 reacts with S3N2Cl2 to give 1a , and with [Me3SiN]2S to give [Cl3MoN]x, while WCl6 yields Cl4WNSCl with S3N2Cl2, and 2a with [Me3SiN]2S. [Cl3MoN ]x does not react with S4N4, but [Cl3WN]x forms 2a. Reactions of VCl4 and VOCl3 with [Me3SiN]2S give [Cl2V S2N3]x, 3. 2c has also been obtained by the reaction of [Ph4As+][Cl5WNSCL-] with [Me3SiN]2S. The oxidation states of the metal atoms are +6 for 1a-c and 2a-c, and +5 for 3, respectively; as determined by 51V and 95Mo NMR spectroscopy and magnetic susceptibility measurements. The UV/VIS spectra of 1b , 1c , 2b, c and 3 are discussed. The electrical conductivity of 3 is reported.

Silver catalysed macrocyclic ether formation: crystal structure of [(CH2O)6Ag2][Ag][AsF6]3

Crystals containing the [(CH2O)6Ag2]2+ cation, which possesses approximate D3d symmetry with the two silver atoms each co-oriented by alternate oxygens of a novel twelve membered macrocyclic ether, were isolated from the reaction of (CH2O)3 with AgAsF6.

Reaktionen von 1,2,4-Thiadiazol-3,5-dicarbonitril mit Schwefelchloriden: Röntgenstrukturanalyse von S3(CN)4Cl2·AsF5 und S3(CN)8Cl2/Reactions of 1,2,4-Thiadiazol-3,5-dicarbonitrile with Sulfur Chlorides: X-Ray Crystal Structure Analysis of S3(CN)4Cl2·A sF5 and S3(CN)8Cl2

The reactions between 1,2,4-thiadiazol-3,5-dicarbonitrile, S(CN)4, and sulfur chlorides (SCl2 and S2Cl2) in the presence of Adogen® 464 (Aldrich) proceeds with formation of S3(CN)4Cl2 (1) and S3(CN)8Cl2 (2). These main products were characterized by X-ray structure determination of an adduct 1a and of 2. This adduct 1a was obtained by addition of the Lewis acid AsF5 in liquid SO2. 1a crystallizes with one SO2 molecule in the space group P21/n with a = 1177.3(2), b = 1082.8(1), c = 1255.3(5) pm, β = 109.73(3)°, Z = 4, V = 1.5061 nm3. It contains two five-membered rings connected by a nitrogen atom. AsF5 is coordinated to one of the ring nitrogen atoms [N(1)] adjacent to the sulfur atom S(1) and C(1)Cl-group. The other ring contains an S(2)-S(3) bond of length 207.7(4) pm. The rings are planar within experimental error. 2 crystallizes in the space group P21/n with a = 782.12(6), b = 1498.1(5), c = 1217.8(2) pm, β = 102.43(1)°, Z = 4, V = 1.3934 nm3. 2 is formed by addition of one molecule of SCl2 to two molecules of S(CN)4.

Darstellung und Eigenschaften des Tribrom-cyclo-1λ6-wolfram-3,5-dithia-2,4,6-triazens/Synthesis and Properties of Tribromo-cyclo-1λ6-tungsten-3,5-dithia-2,4,6-triazene

The metallacycle [Br3WS2N3] has been obtained from the reaction of S4N4 with WBr5. The salt [Ph4P+][Br4WS2N3-] was formed from [Br3WS2N3] by addition of Ph4PBr. It crystallizes in the orthorhombic space group Pbca with a = 1396.8(4), b = 1961.9(5), c = 2108.0(4) pm, and Z = 8. The following mean bond lengths were observed in the anion: W-N 184.2, W-Br 256.8, N-S 157.8 pm.

The first complexes of cyanogen halides with silver(I): crystal structure of [Ag(NCCl)2][SbF6]

The reactions of Ag[AsF6] or Ag[SbF6] with ClCN, BrCN, and ICN yield the complexes [Ag(NCCl)2][AsF6], [Ag(NCCl)2][SbF6], [Ag(NCBr)2][AsF6], [Ag(NCBr)2][SbF6], and [Ag(NCl)2][AsF6]. The salt [Ag(NCCl)2][SbF6] was characterized by an X-ray single-crystal structure investigation. The cation is monomeric. The cyanogen halide is bonded to the silver through nitrogen, with Ag–N 2.140(4)A. The co-ordination geometry at silver is exactly linear.

Facile Synthesis and Crystal Structure of [(PhSO2 N)2 WVI Cl2 (CH3CN)2] - the Oxidative Imination of W(CO)6 by N,N-Dichlorophenylsulphonamide

Abstract The reaction of N,N-dichlorophenylsulphonamide with tungsten hexacarbonyl in refluxing CCl4 leads in good yield to the yellow polymeric complex [(PhSO2N)2WCl2]x, which may be converted to the octahedral nitrene complex [(PhSO2N)2WCl2(CH3CN)2] by recrystallisation from acetonitrile. Crystals of the acetonitrile complex are triclinic, space group P 1̅, a = 820.7(2), b = 1128.8(3), c = 1286.9(3) pm, α = 89.25(3), β = 89.54(3). γ = 72.67(2)°, Z = 2, R = 0.027 for 2527 unique observed reflections.

Synthesis and crystal structure of (S3N3O4)2S, a compound with two six-membered rings bridged by a sulphur atom

The compound S4N4O2 reacts with SO2 under mild conditions to yield (S3N3O4)2S, a new bicyclic system with a skeleton consisting only of sulphur and nitrogen atoms. Crystals of this compound are tetragonal, space group P21m, with a=b= 1 183.8(2), c= 493.5(1) pm, and Z= 4. The structure has been refined to R= 0.027 for 637 unique observed reflexions. The molecule possesses crystallographic mm symmetry, with both mirror planes passing through the sulphur atom which links the two six-membered rings. The bond lengths and angles are consistent with the presence of localised sulphur–di-imide (–NSN–) units, the remaining sulphur–nitrogen bonds being essentially single bonds.