Michael Penk

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.

Multiply bridgehead- and periphery-substituted tribenzotriquinacenes - highly versatile rigid molecular building blocks with C-3v or C-3 symmetry

The chemical versatility of tribenzotriquinacenes as building blocks bearing rigid carbon frameworks with convex/concave molecular surfaces is presented. As revealed by X-ray single crystal structure analysis of the centro-methyl derivative, the tribenzotriquinacene skeleton adopts a perfect C-3v symmetrical conformation in the solid state. Within the crystal, the molecules are strictly aligned in stacks along the C-3v molecular axis of symmetry, at a distance of 6.0 Angstrom and with zero mutual rum along the axis. Bromination of the three benzhydrylic bridgeheads of the parent tribenzotriquinacene, of its centro-methyl homologue, in particular, and of its centro-ethyl homologue has opened a convenient access to a large variety of three-fold substituted or functionalized derivatives with C-3v Or C; molecular symmetry. Thus, several 1,4,7,10-tetrasubstituted tribenzotriquinacenes have become accessible bearing three hydrocarbon or heteroatomic groups in strictly eclipsed orientation with respect to the central substituent. A number of mono- and difunctionalized methyltribenzotriquinacenes have also been prepared. The potential of directed functionalization of the six peripheral positions of the aromatic rings, and of both the three benzhydrylic bridgeheads and the six peripheral positions of the tribenzotriquinacene framework is demonstrated with 1,4,7,10-tetramethyltribenzotriquinacene. The particular molecular topography of the tribenzotriquinacenes combined with their versatile functionalization renders these compounds promising building blocks for application in molecular and material design

[Ag2(S6)2]2- (with a novel cyclic inorganic ring system), [Ag(S9)]- and (PPh4)(NH4)S7·CH3CN with an unusual conformation of the heptasulfide ion

Determination par diffraction RX des structures cristallines de (PPh 4 ) 2 [Ag 2 (S 9 ) 2 ], (PPh 4 ) [AgS 9 ] et (PPh 4 )(NH 4 ) S 7 .CH 3 CN

(PPH4)2(RES4)CU4I5, A COMPOUND WITH A NOVEL ONE-DIMENSIONAL POLYMERIC ANION

The black compound (PPh4)2(ReS4)Cu4I5·MeCN, containing a polymeric heterometallic chain with very short Re–Cu distances [2.638(4)–2.712(4)A] and the metal centres in very different formal oxidation states (VII, I), is formed by the reaction of (PPh4)ReS4 with Cul and (PPh4)I, and structurally characterized by X-ray diffraction.

(NPr4n)[SRev(S4)(S3CMe2)]: Ein [SRev(S4)2]−-Derivat

SummaryThe preparation of (NPr4n)[SRe(S4)(S3CMe2)] (1), (NPr4n)[SRe(S4)2] (2), (NBu4n)[SRe(S4)2] (3) and a new modification of (PPh4)[SRe(S4)2] (4) are reported, including the X-ray structures of1 and4.

Generating Structural Motifs between Three-Dimensional Solids and Discrete Species Based on the {CuNCS} Unit: (PPh4)[(ReS4)Cu2(NCS)2], (NEt4)2[(ReS4)Cu3(NCS)4], and (PPh4)2[(ReS4)2Cu2(NCS)2]

The reaction of (PPh4)ReS4 or (NEt4)ReS4 with CuNCS (in different solvents and with different relative amounts of reactants) yielded black crystals of (PPh4)[(ReS4)Cu-2(NCS)(2)] (1), (NEt4)(2)[(ReS4)Cu-3(NCS)(4)] (2) and (PPh4)(2)[(ReS4)(2)Cu-2 (NCS)(2)] (3). Compound 1 crystallizes in the monoclinic space group P2(1)/n [a = 21.488(6) Angstrom, b = 11.142(4) Angstrom, c = 12.860(5) Angstrom, beta = 90.66(3)degrees, V = 3079(2) Angstrom(3), Z = 4, R = 0.058 and R-w = 0.063 for 5802 reflections with F>4 sigma(F)], compound 2 in the monoclinic space group P2(1)n [a = 10.551(4) Angstrom, b = 14.849(6) Angstrom, c = 22.782(11) Angstrom, beta = 92.35(4)degrees, V = 3566(3) Angstrom(3), Z = 4, R = 0.078 and R-w = 0.056 for 3006 reflections with F > 4.5 sigma(F)] and compound 3 in the triclinic space group P (1) over bar [a = 10.901(3) Angstrom, b = 10.981(3) Angstrom, c = 12.296(3) Angstrom, alpha = 109.20(2), beta = 96.40(2), gamma = 98.17(2)degrees, V = 1356.0(6) Angstrom(3), Z = 1, R = 0.056 and R-w = 0.061 for 5016 reflections with F > 4 sigma(F)]. The structure of the anion in 1 consists of pairs of infinite CuNCS zigzag chains connected by ReS4- groups, thus generating twelve-membered rings running almost parallel to the b axis. In 2, one Cu(NCS)(2) and two Cu(NCS) units are linked by ReS4- groups leading to twelve-membered and novel, unusual sixteen-membered rings alternately arranged in a linear strand. In the discrete complex of 3, two terminal ReS4- groups stabilize one eight-membered (CuNCS)(2) ring. An interesting aspect of the present chemistry is the possibility of excision or linking of fragments from a solid-state structure (CuNCS) in which robust entities are interlinked in different ways.

THE REACTIONS OF DIOXOBIS(ACETYLACETONATO)MOLYBDENUM, MOO2(ACAC)2, WITH TETRATHIOMOLYBDATE AND TETRATHIOTUNGSTATE. HIGH FORMATION TENDENCY OF THE MVI( MU -S)2MOIVO(MU -S)2MVI GROUP AND THE MVIS3(S2)2-TYPE LIGAND (M=MO, W)

1 Tetraphenylphosphonium tetrathiometalates, (PPh4)2MS4 (M = Mo, W), react with MoO2 (acac)2 (2:1) in boiling acetonitrile in redox processes to give mixed-crystal compounds (as expected) of the approximate composition (PPh4)2[Mo3O1.9S8.1] (1) and (PPh4)2[Mo1.4W1.6O1.3S8.3] (2), respectively. and 2 were characterized by single crystal X-ray structure analyses. The various anions o f 1 and 2 contain {MVI(μ-S)2MoIVO (μ-S )2MVI} cores (M = Mo (1); Mo, W (2); bond angle M ··· Mo ··· M = 151.3° (1) 152.2 - 154.3° (2)), which have high formation tendencies. The terminal positions are occupied by S and O atoms. The trinuclear anions of 1 correspond to the type [XYMo(μ-S)2MoO(μ-S)2MoSX ]2- (X = O, S; Y = S, S2). In 2 there are two sets of anions of the type [XYM(μ-S)2MoO(μ-S)2WS2]2- and [ZSM (μ-S)2MoO(μ-S)2MZS]2- (Z = Sn/Om) in the ratio o f 2:1, occupying two symmetry-independent sites in the unit cell. Complex 2 is the first structurally characterized mixed-metal Mo - W thiometalate.