Uwe Schimanski

The preparation of different types of polynuclear transition metal sulfur compounds by thiometallates, including cubane-like ones. Crystal structures of {Cu3WS3Cl}(PPh3)3S, {Cu3WS3Cl}(PPh3)3O, {Cu3MoS3Cl}(PPh3)3S, {Cu3MoS3Cl}(PPh33O, (PPh3)3Cu2WS4·0.8CH2Cl2 and (PPh3)3Ag2MoS4·0.8CH2Cl2

Abstract The following compounds have been prepared by reaction of aqueous solutions of MS 2− 4 and MOS 2− 3 (M = Mo, W) with dichloromethane solutions of CuCl 2 ·2H 2 O (or AgNO 3 and PPh 3 : {Cu 3 WS 3 Cl}(PPh 3 ) 3 S (I), {Cu 3 WS 3 Cl}(PPh 3 ) 3 O (II), {Cu 3 MoS 3 Cl}(PPh 3 ) 3 S (III), {Cu 3 MoS 3 Cl}(PPh 3 ) 3 O (IV), (PPh 3 ) 3 Cu 2 WS 4 ·0.8CH 2 Cl 2 (V) and (PPh 3 ) 3 Ag 2 MoS 4 ·0.8CH 2 Cl 2 (VI). The crystal and molecular structures of I–VI were determined from single crystal X-ray diffractometer data. I–IV crystallize in the orthorhombic space group P2 1 2 1 2 1 with four molecules in the unit cell (I: a = 13.002(2), b = 17.851(2), c = 22.682(2) A, V = 5264.2 A 3 , d calcd = 1.67 g cm −3 ; II: a = 12.825(2), b = 17.529(4), c = 22.711(4) A, V = 5105.5 A 3 , d calcd = 1.70 g cm −3 ; III: a = 12.991(2), b = 17.833(2), c = 22.674(3) A, V = 5253.1 A 3 , d calcd = 1.56 g cm −3 ; IV: a = 12.839(2), b = 17.553(3), c = 22.761(3) A, V = 5129.5 A, d calcd = 1.58 g cm −3 . The structures were refined to final R values of 0.063 (I), 0.071 (II), 0.063 (III) and 0.062 (IV) for 5073 (I), 5349 (II), 3537 (III) and 3016 (IV) independent data. The structure can be described as a strongly distorted cube, four corners being formed by the MS 2− 4 or MOS 2− 3 ligand (with a terminal S or O atom). The remaining corners are occupied by one chlorine and three copper atoms (with one PPh 3 ligand bonded to each of the latter). V and VI crystallize in the monoclinic space group P 2 1 /c with four molecules in the unit cell (V: a = 18.372(6), b = 16.702(7), c = 17.740(8) A, β = 95.56(3)°, V = 541.9 A 3 , d calcd = 1.50 g cm −3 ; VI: a = 18.154(4), b = 17.322(3), c = 17.790(3) A, β = 95.11(2)°, V = 5572.0 A 3 , d calca = 1.46 g cm −3 . The structures were refined to final R factors of 0.109 (V) and 0.084 (VI) for 4844 and 5590 independent reflections respectively V and VI have a structure with a doubly bridging MS 2− 4 ligand, generating a nearly linear M′⋯M⋯ M′P moiety with one tetrahedrally and one trigonally planar-coordinated M′ (M′ = Cu, Ag) atom. The generation of different types of polynuclear compounds by thiometallates containing Cu + and Ag + (including those with the biometals Cu and Mo) and the bioinorganic relevance is discussed.

Darstellung und Röntgenstrukturanalyse von 26 Thiomolybdato- bzw. Thiowolframato-und eines Selenowolframato-Komplexes

SummaryThe preparation and characterization by X-ray structure analysis of the following chalcogenometalato complexes are reported: 1: [(Ph3P)2N]2(NEt4)[Fe(WS4)2]·2MeCN; 2: [(Ph3P)2N]2(NEt4)[Cu(WS4)2]·2MeCN; 3: [(Ph3P)2N]2(NEt4)[Ag(MoS4)2]·MeCN; 4: [(Ph3P)2N]2(NEt4)[Ag(WS4)2]·MeCN; 5: (PPh4)2[Hg(WS4)2]; 6: (PPh4)2[Au2(WOS3)2]; 7: (PPh4)4[Pb2(MoS4)4]; 8: (PPh4)4[Pb2(WS4)4]; 9: (NEt4)2[Fe(WS4)2(H2O)2]; 10: [Fe(DMSO)6][Cl2Fe(MoS4)]; 11: [Fe(DMSO)6][Cl2Fe(MoOS3)]; 12: (PPh4)(NMe3CH2Ph)[Cl2Fe(WS4)]; 13: [Fe(DMF)6][Cl2Fe(WS4)]; 14: (PPh4)2[Cl2Fe(WS4)]; 15: (PPh4)2[Cl2Fe(WS4)]·2 CH2Cl2; 16: (PPh4)2[NCCu(MoS4)]; 17: (PPh4)2[NCAg(MoS4)]; 18: (PPh4)2[NCAg(WS4)]; 19: (PPh4)2[Cu3Cl3(MoOS3)]; 20: (PPh4)2[Cu3Br3(MoS4)]·MeCN; 21: (PPh3)3Cu2(MoOS3)·0.8 CH2Cl2; 22: (PPh3)3Cu2(WOS3)·0.8 CH2Cl2; 23: {Cu3MoS3Br}(PPh3)3O·0.5Me2CO; 24: (PPh3)3Ag2(WSe4)·0.8 CH2Cl2; 25: [(Ph3P)2N]2(NEt4)2[Fe2S2(WS4)2]·3MeCN; 26: (PPh4)2[MoO(MoS4)2]; 27: (PPh4)2[Br2Fe(WOS4)]·DMF.

Zweikern-Komplexe des Wolframs und Molybdäns mit zentraler {XMS2MX}2+-Einheit (X=O, S) und S22−-bzw. S42−-Liganden

The synthesis and crystal structures of the compounds [PPh4]2[W2S12]·0.5DMF, [PPh4]2[W2O2S10]·0.5DMF, [PPh4]2[W2S10]··0.5DMF, [PPh4][NEt4][Mo2OS7]·CH3CN, and [PPh4]2[Mo2O2S10] are reported.

Molybdenum–copper–sulphur-containing cage system and its bioinorganic relevance. Preparation and X-ray crystal structure of (Cu3MoS3Cl)(PPh3)3S with an interesting stereochemistry of non-equivalent Cu atoms

The preparation and structural characterization of (Cu3MoS3Cl)(PPh3)3S, which has a molybdenum–copper–sulphur-containing pseudo-cubane type cage structure and which is a model for Cu–Mo–S interactions in biochemical processes, is reported; the stereochemistry of the three non-equivalent Cu atoms is unusual with the co-ordination of copper ranging from strongly distorted tetrahedral to pseudo-trigonal planar.

Schwefelreiche spirozyklische Komplexe: [Zn(S6)2]2–, [Cd(S6)2]2–, [Hg(S6)2]2– und [Hg(S4)2]2– / Sulfur-Rich Spirocyclic Complexes: [Zn(S6)2]2-, [Cd(S6)2]2-, [Hg(S6)2]2- and [Hg(S4)2]2-

By reaction of Zn(CH3COO)2·2H2O. Cd(CH3COO)2-2H2O, or Hg(CH3COO)2 with defined alcoholic polysulfide solutions the crystalline compounds (NEt4)2[Hg(S6)2] (1), [(PPh3)2N]2[Cd(S6)2]·CH3CN (2), (PPh4)2[Zn(S6)2] (3) and (PPh4)2[Hg(S4)2] (4) could be obtained. 1-4 were characterised spectroscopically (IR, Raman, UV/VIS) and by X-ray structure analyses.

Notizen: Zum Verständnis der zentralen Rolle des Schwefels in Multi-Metall-Aggregaten mit verschiedener Elektronenpopulation: [S2WS2CoS2WS2]n- (n = 2, 3)/On the Central Role of Sulfur in Multi Metal Aggregates with Different Electron Populations: [S2WS2CoS2WS2]n-(n = 2, 3)

Abstract The hetero metal sulfur aggregates [Co(WS4)2] n- (with variable electron population: n = 2, 3) could be isolated as salts and characterized by physical measurements (in-cluding X-ray structure analysis). Experimental and theoretical investigations show that due to a strong metal → ligand electron delocalisation WS42-(like MOS42-) is a non-innocent ligand and that the additional charge upon reduction is located mainly at the S atoms of the ligand system.