bluuebunny/crossref_metadata_2025 huggingface dataset:
Zwei- und dreikernige Fluorooxoanionen des Molybdäns und Wolframs. Kristallstrukturen von K2(NMe4)[MoV
2O2F9]·H2O und (NMe4)2[MoVI
2O4F6(H2O)] / Di- and Trinuclear Fluorooxoanions of Molybdenum and Tungsten. Crystal Structures of K2(NMe4)[MoV
2O2F9]·H2O and (NMe4)2[MoVI
2O4F6(H2O)]
Authors: Leimkühler Manfred , Buchholz Norbert , Mattes Rainer
Published: March 2015

From aqueous HF solutions the following fluorooxo complexes have been obtained: K2(NMe4)[Mo2O2F9]·H2O (1), K(NMe4)2[Mo3O6F9] (2), (NMe4)2[Mo2O4F6(H2O)] (3), (NMe4)2[W2O4F6(H2O)] (4) and (NEt4)2[Mo2O4F6] (5). The structures of 1 and 3 have been fully determined: Crystal data, 1, orthorhombic, space group Abm 2, a = 632.4(2), b = 2078.8(6), c = 1252.3(4) pm, Z = 4; 949 reflections, R = 0.0203. 3, orthorhombic, space group Pca 21, a = 1086.1(2), b = 1386.1(2), c = 1194.4(2) pm, Z = 4; 1826 reflections, R = 0.0231. 1 and 3 contain dimeric fluoro-bridged anions. The central atoms of 3 (and of the isostructural 4) are unequally coordinated. The anion of 2 is a cyclic fluoro-bridged trimer with cis-dioxo groups in the molecular plane. In the anion of 5 two octahedra share an edge, occupied by fluoro ligands.
Bor-stabilisierte N,O-Carbene, I Triphenylbor-Addukte von Siloxy-und Hydroxyalkylisocyaniden und spontane At-Ylid-Bildung / Boron-Stabilized N.O-Carbenes, I Triphenylboron Adducts of Siloxy- and Hydroxyalkyl Isocyanides and Spontaneous Formation of Ate-Ylids
Authors: Fehlhammer Wolf Peter , Hoffmeister Hans , Stolzenberg Heribert , Boyadjiev Borislav
Published: March 2015

.

Triphenylboron adducts of 2- and 3-hydroxyalkyl isocyanides spontaneously undergo intramolecular cyclization to give oxazolidin-2-ylidene and perhydrooxazin-2-ylidene boron complexes, respectively. The same compounds are obtained by methanolysis of the stable species Ph3B-CNCR1R2CR3R4-OSiMe3 (R1, R2, R3, R4 = H, alkyl) (2a-i) and Ph3B-CN(CH2)3-OSiMe3 (2j)IR, 1H NMR, 13C{H} NMR. and mass spectra of the new compounds are reported.
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXI [1] Synthese und Eigenschaften von (Ether-Phosphan)-Platin-Komplexen / Novel Basic Ligands for the Homogenous Catalytic Methanol Carbonylation, XXI [1] Synthesis and Properties of (Ether-Phosphane) Platinum Complexes
Authors: Lindner Ekkehard , Speidel Robert
Published: March 2015

The (ether-phosphane) complexes cis-Cl2Pt(Ph2P∼D )2 (2a, b) [D = CH2C4H7O (a). C H2C4H7O2 (b)] are obtained by reaction of Ph2P∼D (1a , b) with either K2PtCl4 or Cl2Pt(COD) (COD = 1,5-cyclooctadiene). Both Cl- anions are abstracted from 2a, b using AgSbF6 to give the cationic bischelate complexes

(5a, b). The stepwise cleavage and reform ation of Pt-O bonds in (ether-phosphane) platinum complexes is demonstrated bv the sequence

(6a) → [trans-(Ph2P∼D )2PtCO(Cl)][SbF6] (7 a )→5a, when 5a, 6a, and 7a are reacted with KCl, CO, and AgSbF6 respectively. Reduction of 2a with NaBH4 results in the formation of trans-H2Pt(Ph2P∼D)2 (4a). In the presence of HCl 2a is reformed. Excess NaBH4 or heating of 4a yields the bischelate platinum(0) complex

(3a), which is also isolated by reduction of 2a with sodium amalgam. A general method for obtaining

(3a-c) [D = CH2CH2O CH , (c)] is the substitution of COD in Pt(COD)2 by the ether-phosphanes 1a-c. The structures and bonding properties of the compounds 2-7 are discussed on the basis of their 31P{1H } NMR and IR spectra.
Metallkomplexe mit biologisch wichtigen Liganden, L [1] Palladium(II)-, Platin(II)- und Kupfer(II)-Komplexe von α-Aminosäure-N-Glykosiden und von Fructose-Aminosäuren (Amadori-Verbindungen) / Metal Complexes of Biologically Important Ligands, L [1] Palladium(II), Platinum(II) and Copper(II) Complexes of α-Amino Acid-N-Glycosides and of Fructose-Amino Acids (Amadori-Compounds)
Authors: Chen Jingtang , Pili Thomas , Beck Wolfgang
Published: March 2015

Various N-glycosides derived from glucose and α-amino acids and the isomeric Amadori compounds form bis(chelate) complexes of copper(II), palladium (II) and platinum (II). The IR spectra indicate that the ligands are coordinated through the amino group and a carboxylate oxygen atom.
Notizen: Synthese und IR-Spektrum von [MoCl4(NCl)]2 / Synthesis and IR Spectrum of [MoC14(NCl)]2
Authors: Frankenau Andreas , Dehnicke Kurt
Published: March 2015

[MoCl4(NCl)]2 has been prepared by the reaction o f molybdenum hexacarbonyl with excess nitrogen trichloride in CCl4 solution; the product is a red, moisture-sensitive crystal powder. Decomposition above 100 °C leads to MoNCl3. According to the IR spectrum, [MoCl4(NCl)]2 is dimerized via chloro bridges, the

group being linear.
Notizen: AgNb3O8-II, eine Hochdruckphase mit neuartiger Tunnelstruktur / AgNb3O8-II, a High-Pressure Phase with a Novel Tunnel Structure Notizen
Authors: Range Klaus-Jürgen , Wildenauer Manfred
Published: March 2015

A quenchable high-pressure phase of AgNb3O8(AgNb3O8-II) could be synthesized at 35 kbar. 1100 °C in a modified Belt-type apparatus. The structure (Ibam, a = 7.343, b = 10.415. c = 7.007 Å , Z - 4) comprises dodecahedra NbO7 and distorted pentagonal bipyramids NbO 7 shared in such a way that elongated hexagonal tunnels along [001] are formed. Ag+-ions are situated within these tunnels. The shortest O-O distances are 2.247(11) Å (shared edges between NbO8 dodecahedra). AgNb3O8-II is metastable at atmospheric pressure and retransforms to the normal pressure phase AgNb3O8-I at 800 °C.
Na5InTe4 und Na5In2Te6 — Erste Beispiele für Neso-sowie Ditelluro-verbrückte Inotelluroindate/Na5InTe4 and Na5In2Te6 — First Examples of Neso-and Ditelluro-Bridged Inotelluroindates
Authors: Eisenmann Brigitte , Hofmann Achim , Zagler Roland
Published: March 2015

Single crystals of the ternary com pounds Na5InTe4 and Na5In2Te6 have been grown from the melt und have been investigated by X-ray single crystal techniques.

Na5InTe4: orthorhombic, space group Pbcn; Z = 8; a = 742.7(4) pm, b = 2015.4(8) pm, c = 1773.3(6) pm; Na5In:Te6: orthorhombic, space group Cmc21; Z = 8; a = 902.1(4) pm, b = 1536.1(5) pm , c = 2356.5(6) pm.

The crystal structure of Na5InTe4 contains isolated InTe4 tetrahedra (mean bond length: 278.8 pm). In the crystal structure of Na5In2Te6 InTe4 tetrahedra are connected through common vertices to "Zweiereinfach"-chains. Two neighbouring chains each are joined further to ribbons through Te -Te bridges between every second InTe4 tetrahedron.
Synthese und Kristallstruktur von l,13-Bis(8-chinolyl)- 1,4,7,10,13-pentaoxatridecan-diquecksilber(I)-diperchlorat
Authors: Brodersen Klaus , Zimmerhackl Jörg
Published: March 2015

1,13-Bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane-dimercury(I)-diperchlorate is formed by the reaction of 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane in ethanol with an aqueous solution of dimercury(I)-diperchlorate.

It crystallizes in the triclinic space group P Ī with a = 1020.6(2), b = 1200.6(8), c = 1441.1(6) pm , α = 69.60(5)°, β = 83.04(13)°, y = 66.53(4)° and Z = 2. The crystal structure was determined by X -ray diffraction and refined to an R-value o f 0.079.

The Hg2
2+ -ion is coordinated to both nitrogen atoms and four oxygen atoms of one molecule of the ligand. By changing four C - O torsional angles from trans to gauche, the ligand adopts a helical, chiral configuration around the Hg2
2+-ion. The CIO4
--ions are not coordinated to the Hg2
2+-ion.
The Reactions of Dioxobis(acetylacetonato)moIybdenum, MoO2(acac)2, with Tetrathiomolybdate and Tetrathiotungstate. High Formation Tendency of the {Mvi(μ-S)2Miv} (μ-S )2MVI} Group and the [MVI,S3(S2)]2- Type Ligand (M = Mo, W)
Authors: Herberhold Max , Jin Guo-Xin , Müller Achim , Penk Michael
Published: March 2015

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.
Convenient Sign Determination of Various Coupling Constants in Alkynylplatinum(II) Phosphine Complexes
Authors: Wrackmeyer Bernd
Published: March 2015

(1)

The utilization of two-dimensional (2 D) 13C /1H , 31P/1H and 195Pt/1H heteronuclear shift correlations for the sign determination of various coupling constants [e.g., 2J(31PPt13C) > 0 (trans), 2J(31PPt13C) < 0 (cis), 3J( 31PPtC13C) > 0 (cis, trans), 4J(31PPtCC1H ) > 0 (trans), 4J(31PCC1H ) < 0 (cis), 3J(195PtCC1H ) > 0, 2J(31PC1H ) < 0, etc.] is demonstrated, using standard equipment. The complexes [trans-(Bu3P)2Pt(C ≡ C -H)2] and [cis-(Et2PCH2CH2PEt2)Pt(C ≡ C - H)2] (2) serve as model compounds.
UV Photoelectron Spectra and Pseudopotential “ab initio” Calculations of Some 4-Membered Cyclic Amides of Group XIV Elements
Authors: Andreocci Marco V. , Cauletti Carla , Stranges Stefano , Wrackmeyer Bernd , Stader Carin
Published: March 2015

Gas-phase He I and He II photoelectron spectroscopy and Pseudopotential “ab initio” calculations were used to determine the electronic structure of some 4-membered cyclic amides containing Si, Sn and Pb.

The IE splitting on the non-bonding nitrogen-localized m .o .s ., nN
asym(a2) and nN
sym(b2), due to the “through space” interaction is critically affected by the planar ring molecular structure and the coordination of the silicon and tin atoms of the ring.

The pseudopotential “ab initio” model resulted successful in describing the electronic structure of the molecules containing heavy atoms, at a Koopmans’ approximation level.
[Fe4S4l2+-Cluster mit Thioharnstoffliganden: [FeIL3][Fe4S4I3L]' (L = (Me2N)2CS) und [Fe4S4I2L'2](L' = (C4H9NH)2CS)
Authors: Pohl Siegfried , Bierbach Ulrich
Published: March 2015

(1)

The mixed terminal ligand iron-sulfur clusters [F eIL 3][Fe4S4I3L] and [Fe4S4I2L '2] (2) with the neutral ligands L = (M e2N )2CS and L' = (C4H 9N H )2CS have been synthesized by the reaction o f F eI2L2 with 1.5 equivalents o f Fe(C O )5 and 2 equivalents o f sulfur and by the reaction o f F eI2L '2 with 3 equivalents o f Fe(CO)^ and 4 equivalents o f sulfur, respectively. The crystal structures o f 1 and 2 were determined from single crystal X -ray diffraction data. 1 crystallizes in the triclinic space group P 1 with a = 968.6( 1), b = 1466.2( 1), c = 1679.1(1) pm, a = 91.51(1),/?= 93.43( 1), y = 90.82( 1)°, V = 2379.2 * 106 pm 5, Z = 2, R = 0.054. 2 crystallizes in the m onoclinic space group P2 Jn with a = 930.2(1), b = 1666.1(1), c = 2335.6(1) pm, β = 97.26°, V = 3 5 90.8 x 106 pm 3, Z = 4. R = 0.055. The anion [Fe4S4I3L] o f 1 exhibits a nearly undistorted [Fe4S4]2+ core. The F e - S distance to the thiourea ligand is found at 230.6 pm. The m ost striking feature o f the neutral cluster o f 2 is the very short F e - F e distance (268.7 pm) between the iron atom s with thiourea ligation which is possibly a consequence of back-donation. The F e - S thiourea distances in 2 were found to be 230.8 and 231.5 pm , respectively.
Solution and Solid State NMR Spectra of Mono- and Diacetamides Derived from o,o' - Biphenyldiol
Authors: Merwin Lawrence H. , Sebald Angelika , Alt Helmut G. , Lin Whei Oh , Da Costa João Batista Neves
Published: March 2015

o-Hydroxybiphenyl-o'-oxyacetamides and o.o'-biphenyldioxydiacetamides can be prepared from the reaction of o,o'-biphenyldiol and the appropriate chloroacetamide. The products are characterized by their solution (1H , 13C) and solid state (13C) NMR spectra.
Outer-sphere-CT-Wechselwirkungen in organisch-anorganischen Ionenpaaren, IIa. Isolierung metastabiler Precursorkomplexe und thermischer OSCT-Elektronentransfer zwischen einem organischen π-Radikaldikation und Hexahalogeno-selenat(IV)-Komplexen: Erstmalige Erzeugung von SeCl6 ⨪
Authors: Weiss Robert , Grimmeiss Andreas M. H.
Published: March 2015

Deeply coloured 1:1 electrolytes of the type Tris(dimethylamino)cyclopropendiylium )2+SeX6
2- (X = Cl, Br) have been obtained as metastable products of a kinetically controlled redox reaction and are compared with their Tellurium counterparts. According to UV and polarographic evidence there is strong OSCT -interaction between the SOMO of the organic moiety as acceptor and the alg*-HOMO of the ns2 anion as donor. The alg* donor capacity of ns2 anions of type EIX6
2- increases with decreasing atomic weight both of the central atom El and the ligand X. This trend and be rationalized on the basis o f a simple qualitative MO argument.

Upon gentle heating the SeX6
2- systems are oxidized by their own counter cation. The novel SeX6⨪-species thus generated either disproportionates (X = Br) or acts as a selective radical halogenating agent (X = Cl) for the organic cation.
Synthese und Kristallstruktur von Dinatrium-di-μ/-oxo-bis[trihydroxo-methylantimonat(V)] / Synthesis and Crystal Structure of Disodium-di-μ-oxo-bis[trihydroxo-methylantimonate(V)]
Authors: Wieber Markus , Simonis Udo , Kraft Dieter
Published: March 2015

The oxidation of dialkoxymethylstibine with hydrogen peroxide in the presence of sodium hydroxide leads to the formation of disodium-di-μ-oxo-bis[trihydroxo-methylantimonate(V)]. The salt can be synthesized also by dissolving methanestibonic acid in an aqueous solution of sodium hydroxide. The crystal structure has been determined; it shows a dimeric molecule containing a four-membered ring with Sb -O -Sb linkages. Thermal decomposition and spectroscopic properties o f the com pound are discussed.
Synthesis, Properties, and Structure of a Dinitrogen Bridged Dinuclear Hydridocobalt Complex and its Reactions with 1-Alkynes
Authors: Klein Hans-F. , Beck Herbert , Hammerschmitt Birgit , Koch Udo , Koppert Susanne , Cordier Gerhard , Paulus Helmut
Published: March 2015

Dinitrogen bridged cobalt(I) hydride compounds (L3CoH)2 N 2 (1: L = PMe3, 2: 3L = CH3C(CH2PMe2)3 have been synthesized by protonation of dinitrogen cobaltates. 1 crystallizes in the monoclinic space group C 2/m . a = 965, b = 1653, c = 1148 pm ,β = 106.88°, Z = 2. In solution 1 takes up N 2 reversibly forming CoH(N2)(PMe3)3 (1 a) . Infrared data including isotope labeling (15N , 2H) and assignment of vN = N and vCoH bands are presented. 1 reacts with aryl alkynes to give dialkynylcobalt(III) complexes CoH(C2,R1)(C2,R2)(PMe3)3 (5: R 1 = R 2 = C6H5; 6 : R 1 = R 2 = 4 -CH3C6H4; 7: R 1 = R 2 = 4-C lC 6 H 4; 8 : R 1 = C 6 H 5, R 2 = 4-ClC6H4) that are also obtained in a more convenient synthesis involving cobalt(I) intermediates Co(C2R1)(PMe3)4 (10: R 1 = 4 -CH3C6H4, 11: R 1 = 4-ClC6H4). Three metastable isomers of 5 have been characterized, the stable configuration is mer-trans as shown by a crystal structure determination: Space group P 21, a = 933.5(5), b = 1636.7(6), c = 901.1(3) pm, β = 97.4(1)°, Z = 2.
Synthesen und Kristallstrukturen von [Ph3PN PPh3]2[Fe2Se2(Se5)2] · 2 DMF und [Ph3PNPPh3]3[Co3 (Se4)6] · 2 DMF / Syntheses and Crystal Structures of [Ph3PN PPh3]2[Fe2Se2(Se5)2] · 2 DMF and [Ph3PNPPh3]3[Co3 (Se4)6] · 2 DMF
Authors: Müller Ulrich , Ha-Eierdanz My-Linh , Kräuter Gertrud , Dehnicke Kurt
Published: March 2015

The title compounds have been prepared by reactions of sodium polyselenide solutions in DMF with FeCp(CO)2I, and CoCl2 · 6H2O , respectively, in the presence of (Ph3PNPPh3)Cl. They form black crystals, which were characterized by X-ray structure determinations.

[Ph3PNPPh3]2[Fe2Se2(Se5)2] · 2 DMF: Space group P21/c, Z = 2, 2801 observed unique reflexions, R = 0.077. Lattice dimensions at 20 °C: a = 1091.6(7), b = 1247.3(5), c = 3070(2) pm, β = 90.77(4)°. In the dimeric anion the Fe atoms are linked via two bridging Se atoms, and each Fe atom is chelated by an Se5 group. In the crystals, there are alternating layers o f cations and anions.

[Ph3PNPPh3]3[Co3(Se4)6] · 2 DMF : Space group P1̄, Z = 1, 3549 observed unique reflexions, R = 0.108. Lattice dimensions at 20 °C: a = 1496.2(5), b = 1504.8(5), c = 1904.1(6) pm, α = 100.31(2)°,β = 100.60(2)°, γ= 117.18(2)°. In the [Co3(Se4)6]3- ion two [Co(Se4)3]3- units, each with three chelating Se4 groups, are linked to a central Co3+ cation.
6 α-n-Hexyl-1 α-hydroxymethyl-(4aβ, 8aα)-decahydronaphthalen-2 β–ol: Synthese und kristallin-flüssige Eigenschaften eines neuen amphiphilen Diols / 6 α-n-Hexyl-1 α-hydroxymethyl-(4aβ, 8 aα)-decahydronaphthalene-2β-ol: Synthesis and Liquid-Crystalline Properties of a Novel Amphiphilic Diol
Authors: Tschierske Carsten
Published: March 2015

The synthesis of 6 α-n-hexyl-1 α-hydroxymethyl-(4aβ, 8aα)-decahydronaphthalene-2β-ol using a Robinson-Nazarow-anellation followed by a Birch-reduction is described. This compound exhibits liquid crystalline behaviour in the presence of water. No mesomorphic properties were observed in the absence of water.
Diisophorone and Related Compounds, Part 28 [1] Diisophorane-4-spiro-2′-(oxiranes)
Authors: Kurzer Frederick , Morgan Alan R.
Published: March 2015

The action of diazomethane on 3,4-dioxodiisophoranes yields 3-oxodiisophorane-4-spiro- 2′-(oxiranes). Their reactions, spectral properties and fragmentation patterns under electron impact, and those of compounds derived from them , conform to their proposed structures.
Darstellung und Kristallstruktur von 2,4,6-Triferrocenyl- 1,3,5,2,4,6-triselenatriborinan/Synthesis and Crystal Structure of 2,4,6-Triferrocenyl-1,3,5,2,4,6-triselenatriborinane
Authors: Horn Hans , Rudolph Frank , Ahlrichs Reinhart , Merzweiler Kurt
Published: March 2015

The reaction of [(NEt3)FcBBr2] (Fc:C5H5FeC5H4) with bis(trim ethylsilyl)selenane leads to the formation of Fc3B3Se3 (1). 1 crystallizes in the triclinic space group P1̄. The lattice constants (at 210 K) are: a = 1487.8(8) pm , b = 1563.1(8) pm, c = 1588.6(9) pm, ɑ = 107.81(4)°, β = 101.06(4)°, γ = 115.85(4) . 1 contains a nearly planar B3Se3 ring with alternating B and Se atoms. The electronic structure of the model compound Ph3B3Se3 was investigated by ab initio SCF studies.
Manganese(II) Amides: The Synthesis and X-Ray Crystal Structures of Mn[N(SiMe3)(2,6-Pri
2C6H3)]2[THF] and Mn3[N(H)2,6-Pri
2C6H3]4[N(SiMe3)2]2
Authors: Kennepohl Dietmar K. , Brooker Sally , Sheldrick George M. , Roesky Herbert W.
Published: March 2015

A series of manganese(II) am ides (1-4), derived from 2,6-diisopropylaniline (H2NAr; where Ar = 2,6-Pri
2C6H3) and its N-silylated derivative H(SiMe3)NAr, has been prepared and characterized. The crystal structure of Mn[N(SiMe3)Ar]2[THF] (2) reveals a monomeric species with a planar three-coordinate Mn(II) center. Crystal data for 2: trigonal (hexagonal axes), a = 30.119(2) Å, c = 10.589(1) Å, V = 8319(1) Å3, T = 153 K, space group P31 (No. 144), Z = 9 (R/Rw = 0.053/0.050). In contrast, Mn3[N(H)Ar]4[N (SiMe3)2]2 · C7H8 (4) is shown to be a novel trinuclear compound held together by nitrogen-bridges. The two terminal Mn(II) atoms have a distorted trigonal planar arrangement of nitrogen donors whereas the central Mn(II) is surrounded by a distorted tetrahedral array of nitrogen donors. Crystal data for 4: orthorhombic, a = 21.301(5) Å, b = 17.021(6) Å, c = 20.519(7) Å, V = 7439(4) Å3, T = 153 K, space group Pbcn (No. 60), Z = 4 (R/Rw = 0.050/0.070).
Metallkomplexe mit funktionalisierten Schwefelliganden, II . Ruthenium(II)-benzylthiosulfinato Komplexe. Kristallstrukturanalyse von Cp(Ph3P)2Ru[S—S(O)—CH2C6H5]/Metal Complexes of Functionalized Sulfur Containing Ligands, II. Synthesis of Ruthenium (II) B enzyl-thiosulphinato Complexes. X-Ray Structure Determination of Cp(Ph3P)2Ru[S—S(O)—CH2C6H5]
Authors: Weigand Wolfgang , Bosl Gabriele , Robl Christian
Published: March 2015

(2))

CpRu(PPh3)(L)(SH) (L = PPh3 (1), CO compounds react with N-(benzylsulphinyl) phthalim ides to give the chiral complexes CpRu(PPh3)(L)[S-S(O)-CH2-Ph] (4, 5). For 5, a diastereoselectivity of 10:3 is observed. The compounds 4, 5 have been characterized by their spectroscopic data. The X-ray structure d etermination of 4 shows sulphur-sulphur bond lengths of 204,4(4), 205,5(4) and 205,3(4) pm for three independent molecules.
Preparation and Catalase-Like Function of a Binuclear Iron(III) Complex with N,N,N',N'-Tetrakis(2-pyridylmethyl)-2-hydroxy-1,3-diaminopropane
Authors: Nishida Yuzo , Nasu Miyuki , Akamatsu Tetsuya
Published: March 2015

The complex derived from Fe(NO3)3 · 9H2O and perchlorate salt of N,N,N',N'-tetrakis- (2-pyridylmethyl)-2-hydroxy-1,3-diaminopropane (abbreviated as H(HPTP)) is formulated as a binuclear species with μ-alkoxo and μ-hydroxo bridges, [Fe2(HPTP)(OH)(NO3)2 ](ClO4)2, on the basis of analytical data, magnetic properties, and conductivity data. This complex reacts with hydrogen peroxide in water to form a violet adduct with new charge transfer bands in the range 520-600 nm. This adduct is very unstable at room temperature, indicating the high catalase-like function of this complex. The complex exhibits a high ability to degradate DNA in the presence of H2O2. The observed high catalase-like and bleomycin-like functions of the complex are discussed in terms of the activation of the peroxide ion by the binuclear iron(III) compound.
Darstellung und Kristallstruktur von Rb2Sn2Se5, ein Rubidium- Selenostannat(IV) mit Raumnetzstruktur/Preparation and Crystal Structure of Rb2Sn2Se5, a Rubidium Selenostannate(IV) with Framework Structure
Authors: Sheldrick W. S. , Braunbeck H.-G.
Published: March 2015

Methanolothermal reaction of Rb2CO3 with SnSe2 in the presence of BaSe at 160 °C and 13 bar yields Rb2Sn2Se5, the structure of which was established by X-ray analysis. The crystal structure contains polyanions [Sn2Se5
2-]∞, which display a framework structure. The anion structure is built up from trigonal SnSe5 bipyramids, linked together via one corner and two edges. This leads to the formation of channels parallel to the b-axis, which contain the rubidium cations. The crystal structure is isostructural to that of Tl2Sn2S5.
Kristallstruktur von Acetonitril-trichlorocobaltat(II) Synthese und Struktur von 2,6-Dimorpholino-4-phenyl-1,3,5-oxadiazinium-Salzen / Crystal Structure of Acetonitrile Trichlorocobaltates(II) Synthesis and Structure of 2,6-Dimorpholino-4-phenyl-1,3,5-oxadiazinium Salts
Authors: Hartung Jürgen , Beyer Lothar , Gutiérrez-Puebla Enrique , Fernández Vicente
Published: March 2015

Reactions of tris[(N-morpholinothiocarbonyl)benzamidato]cobalt(III) and of the free ligand in the presence of CoCl2, with SOCl2 in acetonitrile yield stable acetonitrile trichlorocobaltate(II) salts with 2,6-dimorpholino-4-phenyl-1,3,5-oxadiazinium cations, suitable for X-ray structure determination. Space group P21,/n, Z = 4, 4387 observed unique reflexions, R = 0.049, Lattice dimensions (22 °C): a = 772.94(9), b = 1611.5(4), c = 1911.1(5) pm; β = 96.23(2)°.
Löslichkeit und Dehydratisierungsprozesse bei MeSO4 · nH2O (Me = Fe, Co, Ni, Zn, Mg; n = 7,6,4,1) in Methanol und Ethanol / Solubility and Dehydration of MeSO4 · nH2O (Me = Fe, Co, Ni, Zn, Mg; n = 7, 6, 4, 1) in Methyl and Ethyl Alcohols
Authors: Maneva M. , Rizova D.
Published: March 2015

A study has been made of the solubility of MeSO4 · nH2O (Me = Fe, Co, Ni, Zn, Mg; n = 7, 6 , 4, 1) in the organic solvents CH3OH and C2H5OH in the temperature interval of 20 - 50 °C. The data obtained are presented with the polytherms of solubility and the equilibrium hydrates for particular conditions have been identified. The densities of the respective liquid phases have also been determined. The dependence between lgS = f(l/ε0) has been indicated for some o f the systems.
Synthese, FIR-Spektren und Kristallstrukturen der Pentaselenide K2Se5 und [Na(15-Krone-5)]2Se5 / Syntheses, FIR Spectra, and Crystal Structures of the Pentaselenides K2Se5 and [Na(15-crown-5)]2Se5
Authors: Müller Volker , Frenzen Gerlinde , Dehnicke Kurt , Fenske Dieter
Published: March 2015

K2Se5 has been prepared by crystallization from a potassium polyselenide solution in DMF. In a similar way [Na(15-crown-5)]2Se5 can be prepared by crystallization from a sodium polyselenide solution in DMF in the presence of 15-crown-5. Both compounds were characterized by FIR spectroscopy as well as by X-ray structure determinations.

K2Se5: Space group P 212121, Z = 4, 1659 observed independent reflections, R = 0.061. Lattice dimensions at - 90 °C; a = 671.5(5), b = 694.9(5), c = 1776.4(9) pm. The compound crystallizes with the K2S5 type structure.

[Na(15-crown-5)]2Se5: Space group P 1̄, Z = 2, 3026 observed indenpendent reflections, R = 0.140. Lattice dimensions at -100 °C: a = 853.7(5), b = 1042.8(10), c = 2011.0(10) pm; α = 88.95(5)°, β = 79.42(5)°, γ = 66.15(5)°. The compound forms an ion triple, in which the sodium ions are coordinated by the five oxygen atoms of the crown ether molecules as well as by the terminal selenium atoms of the pentaselenide chain. The rather high R value is a result of the disordered crown ether molecules.
Elementorganische Verbindungen mit o-Phenylenresten, XXIII [1] 2,3,6,9,10,13-Hexamethoxy-5,7,12,14-tetrathia-5,7,12,14-tetrahydropentacen - 2.3-Dichlor-5,6-dicyan-1,4-benzochinon (1/2) / Organometalloidal Compounds with o-Phenylene Substituents, XXIII [1] 2,3,6,9,10,13-Hexamethoxy-5,7,12,14-tetrathia-5,7,12,14-tetrahydropentacene - 2.3-Dichloro-5,6-dicyano-1,4-benzoquinone (1 /2)
Authors: Berges Peer , Mansei Volker , Klar Günter
Published: March 2015

The title compound is prepared by combining hot solutions of the components. X-ray analysis shows hexamethoxytetrathiatetrahydropentacene to act as a bifunctional donor, each of its dimethoxybis(organylthio)benzene units being in contact with a dichlorodicyanoquinone molecule. In the crystal stacks of the type DA2 ,DA2, ··· with an alternating arrangement o f donor and acceptor molecules are formed. In the complex the donor has a cis -conformation (boat form) in contrast to its pure form where the trans-conformation (chair form) is found.
Oligophosphan-Liganden, XXXIV** Organoplatin(II)-Komplexe mit (+)-(l S)-1,2-Bis(diphenylphosphino)- 1 -phenylethan-Koordination / Oligophosphine Ligands, XXXIV** Organoplatinum(II) Complexes with (+)-(1S)-1,2-Bis(diphenylphosphino)- 1-phenylethane Coordination
Authors: Saare Andrea , Dahlenburg Lutz
Published: March 2015

Reaction of (C8H12)Pt(CH2CMe3)2 with ( + )-(1 S)-Ph2PCH(Ph)CH2PPh2, S-PHEPHOS, gave (S-PHEPHOS)Pt(CH2CMe3)2 (1). Cleavage of one of the Pt-C bonds of this compound with methanolic HCl yielded (S-PHEPHOS)PtCl(CH2CMe3) (2) which could be converted to (S-PHEPHOS)PtH(CH2CMe3) (3) by treatment with Na[HB(OMe)3], The complexes so obtained were characterized by NMR spectroscopy (preferentially 31P) as well as by an X-ray structure analysis performed on the dineopentyl derivative 1. While thermal generation of (S-PHEPHOS)Pt(0) from 3 in the presence of HC ≡ CC(O)OCMe3 produced the alkyne coordination compound (S-PHEPHOS)Pt(HC ≡ CC(O)OCMe3) (4) efficiently, thermolysis of 3 in the presence of PhC ≡ CH resulted in smooth trapping of the 14e intermediate to form the product of oxidative C - H addition, (S-PHEPHOS)PtH(C≡CPh) (5). In contrast, only indiscriminate reactions were observed to occur on thermal generation of (S-PHEPHOS)Pt(O) from neopentyl hydride 3 in C6H6 at 70 °C.
Clathrathydrate von Tetramethylammoniumhydroxid: Neue Phasen und Kristallstrukturen [1] / Clathrate Hydrates of Tetramethylammonium Hydroxide: New Phases and Crystal Structures [1]
Authors: Mootz Dietrich , Stäben Dieter
Published: March 2015

The melting diagram of the system tetramethylammonium hydroxide-water has been reinvestigated in the region of 66.67 - 100 mol% H2O , using DTA , DSC and temperature-dependent X-ray powder diffraction. This was done as correction and supplementation of a previous study in the same laboratory (D. Mootz, R. Seidel, J. Incl. Phenom. 8 , 139 (1990)). The system is now considered to contain as many as eight stable hydrates, three of them dimorphic with a low-temperature α and a high-temperature β form. The compositions are Me4NOH · χH2O with χ = 2 (α and β), 4, 4.6 (α and β), 5 (α and β), 6.67, 7.5, 8.75 and 10. A second 7.5-hydrate, called 7 .5 α in the previous study, is now regarded as metastable. - Structure determinations have been performed for the new phases with x = 4.6 (α), 6.67 and 8.75. The 4.6 α-hydrate, transforming to 4.6 β at 32 °C, is cubic with space group Pa3̄ and Z = 40 formula units per unit cell. The lattice constant is a = 21.493 Å at -160 °C. The 6.67-hydrate, melting with decomposition at 13 °C, is monoclinic with space group P21/m and Z = 6 . It was studied as the O-deuterated isotype with unit-cell dimensions a = 11.874, b = 20.019, c = 8.272 Å and β = 103.84° at 3 °C. The 8.75-hydrate, melting with decomposition at - 3 °C, is cubic with space group 14̄3 d, Z = 16 and a = 18.38(2) Å at - 20 °C. The three structures, as most others of the higher hydrates of the system studied previously, are those of polyhedral clathrate hydrates. For the hydrates 4 .6 α and 6.67 deviations of the anionic, i.e. proton-deficient, new water structures from being fully four-connected are described in detail. The 8.75-hydrate is isostructural with the hitherto unparalleled 9.75-hydrate of t-butyl amine. - The phase identity and structure of the 4.6 β-hydrate were recognized as those attributed to an erroneously assumed 5 β-phase in the previous study. 5 β now denotes the room-temperature form of the pentahydrate, previously called 5 α. The present 5 α is another of the new phases and the only one of the system with its structure still undetermined.
Novel C-Geranyl 7-Hydroxycoumarins from the Aerial Parts of Eriostemon tomentellus
Authors: Rashid Mohammad A. , Armstrong James A. , Gray Alexander I. , Waterman Peter G.
Published: March 2015

From the aerial parts of Eriostemon tomentellus five coumarins have been isolated. These have been characterized as ostruthin (6-geranyl-7-hydroxycoumarin (1)) and the novel compounds, 8-geranyl-7-hydroxycoumarin (2), (E)-6-(7-hydroxy-3,7-dimethylocta-2,5-dienyl)- 7-hydroxycoumarin (3), (E)-6-(7-hydroperoxy-3,7-dimethylocta-2,5-dienyl)-7-hydroxycoumarin (4), and 6-(6-hydroxy-3,7-dimethylocta-2,7-dienyl)-7-hydroxycoumarin (5). In addition tembamide (2-{4-methoxyphenyl}-2-hydroxy-N-benzoylethylamine (6 ) was isolated and the l3C NMR spectrum reported for the first time.
Elektronentransfer und Ionenpaar-Bildung, 27 [1, 2] Darstellung von Semichinon-Ionenpaaren durch Reduktion von Chinonen mit Tetraalkylammonium-boranat in aprotischen Lösungen: 1,10-Phenanthrolin-5,6-dion / Electron Transfer and Ion Pairing, 27 [1, 2] Preparation of Semiquinone Ion Pairs by Reduction of Quinones Using Tetraalkylammonium Boranate in Aprotic Salt Solutions: 1,10-Phenanthrolin-5,6-dione
Authors: Bock H. , Hänel P.
Published: March 2015

Ion pairs of 1,10-phenanthrolin-5,6-dione radical anion [M · ⊖Me⊕n] ·⊕(n−1) with Me⊕n = Mg⊕⊕, Ca⊕⊕, Sr⊕⊕, Zn⊕⊕, Cd⊕⊕, Pb⊕⊕ and La⊕⊕⊕ are advantageously prepared in aprotic DMF solution containing appropriate metal salts Me⊕nX⊖ by using the ‘mild’ single-electron reducing agent tetra(n-butyl)ammonium-boranate R4N⊕BH4
⊖ . For comparison, the ‘naked’ radical anion with the largely interaction-free [K⊕(2.2.2)-cryptand]⊕ counter cation is chosen, which is formed on reduction with potassium in THF solution of (2.2.2)-cryptand. Addition of excess Na⊕[B(C6H5)4]⊖ to the reduction solution only yields a solvent-separated ion pair (M · ⊖)DMF ··· (Na⊕)DMF, whereas in the presence of multiply charged counter cations Me⊕n the respective contact ion pair radical cations [M · ⊖Me⊕n] · ⊕(n−1) are formed. Their g values decrease with increasing nuclear charge of Me⊕n and their metal-s-spin densities increase with the effective counter cation charge n⊕/rMe⊕n. The ESR /ENDOR data recorded suggest Me⊕n complexation by the δ⊖OC -COδ⊖ chelate tongs and the ion pair stability, which is modified by the dielectric properties of the solvent used, may be rationalized by the Coulombic attraction between the radical anion M · ⊖ and the counter cations Me⊕n.
Reaktionen von CF3SF: Addition an C=S-Doppelbindungen / Reactions of CF3SF: Addition to C = S Double Bonds
Authors: Gombler Willy , Bollmann Gerd
Published: March 2015

Trifluoromethanesulfenylfluoride, CF3SF, adds to the carbon-sulfur double bond to form fluorinated compounds containing a trifluoromethyldisulfanyl group. Reactions of CF3SF with CS2,CF2S,CCl2S and (CF3S)2CS are described.
1.4.2-Diazaphospholo[4,5-a]pyridine / 1.4.2-Diazaphospholo[4,5-a]pyridines
Authors: Karaghiosoff Konstantin , Bansal Raj K. , Gupta Neelima
Published: March 2015

Condensation o f 1-alkyl-2-aminopyridinium halides 1 with PCl3 in the presence of NEt3 yields, depending on the 1-substituent, pyridinylidene am inodichlorophosphines 2 or 4H-1,4,2-diazaphospholo[4,5-a]pyridines 3. The products are characterized by 31P, 1H and 13C NMR. Dimethylsulfate methylates the diazaphospholopyridines 3 at N-1.
Electron-and Ligand-Transfer Reactions Involving N,N-Dialkylcarbamates. Synthesis and Molecular Structure of V2[η5-(C5H5)]2[O2CN(C2H5)2]4
Authors: Calderazzo Fausto , Pampaloni Guido , Sperrlea Martin , Englert Ulli
Published: March 2015

Electron-and ligand-transfer reactions of low-valent organometallic compounds of titanium and vanadium with N,N-dialkylcarbamates of titanium(IV) are reported. The reaction of VCp2 (Cp = η5-cyclopentadienyl) with Ti(O2CNEt2)4 affords, inter alia, the dimeric vanadium(III) N ,N-diethylcarbamato derivative V2Cp2(O2CNEt2)4 which has been studied by X-ray diffraction methods. Crystal data; triclinic, space group P1̄ ; a = 10.802(2), b = 11.004(1), c = 8.960(1) Å; α = 112.879(9), β = 102.66(1), γ = 102.42(1)°; V = 902.3(6) Å3; Z = 1; F(000) = 368, ρcalc = 1.282 g cm-3; μ = 5.47 cm-1. It consists of a centrosymmetric dimer, the two vanadium atoms being surrounded by four oxygen atoms of the bridging N,N-diethylcar-bamato groups and by the cyclopentadienyl ligand. The metal atom exhibits a distorted square-pyramidal coordination geometry with the oxygen atoms occupying the basal plane. The reaction of TiCp2(CO)2 or Vmes2 (mes = η6-1,3 ,5 -Me3C6H3) with Ti(O2CNEt2)4 affords Ti(III) and V(III) N,N-diethylcarbamato derivatives by a simultaneous ligand-and electron-transfer reaction. Magnesium N ,N-diisopropylcarbamate, Mg(O2CNPri
2)2, has been obtained by a ligand-transfer reaction between MgCp2 and Ti(O2CNPri
2)3.
Metallionen als Löscher der Huminstoff-Lumineszenz / Metal Ions as Quencher of the Luminescence of Humic Substances
Authors: Scheck Christoph F. , Frimmel Fritz H. , Braun André M.
Published: March 2015

The luminescence of aquatic humic substances in water is quenched over a broad range of pH by paramagnetic metal ions like iron(II) and manganese(II). The efficiency dependents on the pH of the solution and rises with increasing basicity; this parallels the complexing of metal ions by humic substances. No quenching of the luminescence is observed by the addition of aluminium(III).
Pyridazine Derivatives and Related Compounds, Part 4. Pyrrolo[2,3-c]pyridazines and Furo[2,3-c]pyndazines, Synthesis and Some Reactions
Authors: Deeb Ali , Bayoumy Besher , Yasine Fathy , Fikry Rida
Published: March 2015

Ethyl 5-amino-3,4-diphenyl-7H-pyrrolo[2,3-c]pyridazine-6-carboxylate (1), ethyl 5-aminofuro[ 2,3-c]pyridazine-6-carboxylate (2) and 5-aminofuro[2,3-c]pyridazine-6-carboxamide (3), are obtained from 4-cyano-5,6-diphenyl-3(2H)-pyridazinone. 5-Acetamido and 5-chloroacetamido derivatives prepared from 1, undergo cyclization on heating to form 2-substituted pyridazino[4',3':4,5]pyrrolo[3,2-d]oxazin-4(5H)-one (5a, b). The reaction of 1 and 2 with hydrazine gave 6-carbohydrazide derivatives (7 a, b). Compound 3 undergoes condensation with acetyl chloride, chloroacetyl chloride, benzoyl chloride, formamide and carbon disulphide to furnish the corresponding pyrimido[4',5' :4,5]furo[2,3-c]pyridazin-4(3 H)-one derivatives. The reaction of 1 with o-aminophenol gave 3,4-diphenyl-11-oxo-10,11-dihydro-12H -pyridazino[ 4',3' :4,5]pyrrolo[3,2-b][1,5]benzoxazepine.
Calcium-bis[N,N'-bis(trimethylsilyl)benzamidinat]-THF (1/2) - Synthese, spektroskopische Charakterisierung und Struktur/Calcium-bis[N,N'-bis(trimethylsilyl)benzamidinate]-THF (1/2) - Syntheses, Spectroscopic Characterization and Structure
Authors: Westerhausen Matthias , Schwarz Wolfgang
Published: March 2015

The reaction of calcium-bis[bis(trimethylsilyl)amide]-THF (1/2) with benzonitrile in THF nearly quantitatively yields the title compound calcium-bis[N,N'-bis(trimethylsilyl)- benzamidinate]-THF (1/2). Under similar conditions pivalonitrile substitutes an ether ligand of calcium-bis[bis(trimethylsilyl)amide]-DME (1/2) without the formation of the corresponding amidinate derivative. The calcium-di(benzamidinate) [H5C6-C(NSiMe3)2]2Ca · 2THF crystallizes in the space group Pbcn with {a = 188.8(6); b = 1286.0(3); c = 1802.5(5) pm; Z = 4}. The calcium atom is hexa-coordinate with a distorted octahedral trans-configuration and with Ca - O and Ca - N bond distances of 238 and 243 pm, respectively. The bond lengths within the NCN moiety with values of 132 pm are characteristic of a diazaallylic system. The short N - Si bond lengths of about 170.5 pm as well as the high field shift of the 29Si{1H} NMR signal are evidence for an effective backdonation of the anionic charge from the nitrogen to the silicon atoms.
Schwingungsspektren und Normalkoordinatenanalyse der Acetatohalogenodimetallate M2(O2CCH3)4X2, M = Re, Tc; X = CI, Br/Vibrational Spectra and Normal Coordinate Analysis of Acetatohalogenodimetalates M2(O2CCH3)4X2, M = Re, Tc; X = Cl, Br
Authors: Skowronek J. , Preetz W.
Published: March 2015

The orange-red Tc2(O2CCH3)4Br2 has been prepared for the first time by reaction of [Tc2Br8]2- with glacial acetic acid and acetic anhydride. The IR and Raman spectra have been recorded at 80 K and are compared with those of the analogous compounds Tc2(O2CCH3)4Cl2, Re2(O2CCH3)4Cl2 and Re2(O2CCH3)4Br2. The assignment according to the point group D4h is supported by normal coordinate analysis based on a general valence force field. The quadruple M - M bond is stabilized by the bridging acetato and destabilized by the axial halogeno ligands. The valence force constants fd(MM) are determined to 3,96-4,08 mdyn/Å. The interaction constants fdd(MM/MX), fdd(MM/MO) and fdα (MM/MMO) are about three times higher for the technetates as compared with the rhenates. The stronger interaction between oppo­site bonds in the equatorial ligand sphere is revealed by the stretching interaction constants fdd', which are about two times higher than fdd for M - O bonds at right angles. The strong coupling of the ring co-ordinates implies extensive mixing of the M - O valence and deformation modes. The electronic spectra of Tc2(O2CCH3)4X2, agree with those of the corresponding Re compounds.
Cyclometallierung und Entalkylierung eines zweizähnigen Chlorphosphans mit Fe2(CO)9/Cyclometallation and Dealkylation of a Bidentate Chlorophosphine by Fe2(CO)9
Authors: Bitterer F. , Brauer D. J. , Dörrenbach F. , Stelzer O.
Published: March 2015

Treatment of the bifunctional chlorophosphine R2P-CH2-PRCl (R = tBu) with diironenneacarbonyl affords the binuclear complex Fe2(CO)6[μ2,η3-P (tBu )-CH2-P(tBu)-CMe2-CH2] (2) by oxidative addition reaction and metallation of one of the tBu groups within the tBu2P - CH2 unit. At elevated temperatures 2 eliminates isobutene, the phosphido complex Fe2(CO)6[(μ2-P(tBu))2CH2] (3) being formed. The crystal structure of 2 (space group P1̄ with a = 8.663(3), b = 10.849(4), c = 14.618(6) Å, α = 103.02(2), β = 96.32(3), γ = 112.77(2)°, Z = 2) reveals a binuclear complex with a P(tBu) - CH2- P(tBu) - CMe2- CH2 ligand backbone spanning the Fe - Fe bond via a phosphido (μ2-P(tBu)(CH2)) and a phosphinoalkyl (μ2-P(tBu)-CMe2-CH2) bridge. A strained, four-membered P2CFe ring is formed through coordination of the P - C - P donor set to Fe(2).
Preparation and Characterization of New Amino-Substituted Crowns and Podands
Authors: Kılıç Zeynel , Weber Edwin , Gündüz Necla , Kılıç Emine , Nazır Hasan , Hökelek Tuncer , Toy Mehmet
Published: March 2015

A number of macrocyclic (1b-3b) and linear oligoether compounds (4b-8b) with 2,2'- methylenebis(4-aminophenol) or 2-aminophenol characteristic building blocks have been synthesized by reduction of the corresponding nitro derivatives with Pd -C/hydrazine hydrate. The pKa' values of the new compounds have been determined by potentiometric titration. These and the observed spectroscopic data are discussed and compared with related compounds. A crystalline 1:1 complex of the diamino crown 3b with NaSCN has also been prepared and characterized.
Triorganogermanium Selenocarboxylates: Synthesis and Reactions
Authors: Kato Shinzi , Ibi Kazumasa , Kageyama Hideki , Ishihara Hideharu , Murai Toshiaki
Published: March 2015

A series of triphenylgermanium selenocarboxylates 3 were synthesized and characterized. The esters 3 are thermally stable, but labile towards moisture and oxygen. They react with arenesulfenyl chlorides and areneselenenyl bromides at room temperature to afford the corresponding acyl arenesulfenyl selenides and acyl aryl diselenides in moderate yields.
Liquid Crystalline Compounds in the Thiophene Series, Part 5 Synthesis and Characterization of Liquid Crystalline Polysiloxanes with Styrylthiophene Units
Authors: Koßmehl Gerhard , Pithart Cornelia
Published: March 2015

The synthesis and characterization of polysiloxanes containing styrylthiophene units as side groups are described. Polysiloxanes containing spacers with six or eleven methylene units exhibit smectic phases. If the spacer contains only three methylene units, the polysiloxanes exhibit no liquid crystalline behaviour.
Notizen: Über die Kristallstruktur von β-SCl3
+SbCl6
- und interionischen Wechselwirkungen in SCl3
+-Salzen/The Crystal Structure of β-SCl3
+SbCl6
- and Interionic Interactions in SCl3
+ Salts
Authors: Minkwitz Rolf , Kornath Andreas , Preut Hans
Published: March 2015

Chlorosulfonium hexachloroantimonate crystallizes in the monoclinic space group C 2/m with a = 1405.5(3) pm, b = 1055.1(2) pm , c = 882.2(2) pm, β = 110.05(3)° at 169 K with 4 formula units per unit cell. A distorted octahedral coordination around sulphur is formed by three S - C l bonds and three interionic sulphur chlorine contacts. The interionic interactions in SCl3
+ salts of known crystal structures are discussed.
Notizen: Trennung und biologische Wirksamkeit der Enantiomeren eines chiralen Thiadiazolylsulfoxides/Separation and Biological Activity of the Enantiomers of a Chiral Thiadiazolyl Sulfoxide
Authors: Walek Wolfgang , Fieseler Christine , Schneider Peter , Fischer Gerhard W.
Published: March 2015

The enantiomers of the fungicidal and bactericidal (3-chloro-1,2,4-thiadiazol-5-yl)-(3´-chloro-1´,2´,4´-thiadiazoyl-5´-ylthiomethyl)-sulfoxide (2) have been separated by liquid chromatography on triacetylcellulose. Tested in a photometer assay on Torulopsis H 24 and Erwinia carotovorum (+)-2 and (-)-2 show practically the same activity and do not differ from the racemic mixture.
Untersuchungen zur Anionendefektverteilung in Sr2MnO4-y/ Investigation on the Distribution of Anion Vacancies in Sr2MnO4-y
Authors: Kriegel R. , Borrmann H. , Simon A. , Feltz A.
Published: March 2015

At high temperatures Sr2MnO4-y crystallizes in the K2NiF4 structure with anion defects. X -ray structure determination in space group I 4/m m m (No. 139) with a = 380.58(3), c = 1253.19(11) pm reveals the composition Sr2MnO3.84±0.05 for a single crystal prepared under argon at 1510 °C. The oxygen deficiency is restricted to the basal oxygen atoms in the perovskite layer. The X -ray experiment shows a statistical distribution of the defects. They lead to a distorted tetragonal pyramidal coordination of the Mn3+ ions.
Kristallstruktur des Cadmiumthiocyanat-Hexamethylentetramin-Addukts Cd(SCN)2·C6H12N4 · 2H2O/ Crystal Structure of the Cadmium Thiocyanate Hexamethylenetetramine Adduct Cd(SCN )2· C6H12N4 · 2H2O
Authors: Pickardt Joachim , Gong Gill-Taik
Published: March 2015

Crystals of the adduct Cd(SCN )2 ·C6H12N4 · 2H2O were obtained by diffusion of an aqueous solution of hexamethylenetetramine into an aqueous solution of cadmium thiocyanate. The crystals are triclinic, space group P 1̄, Z = 2, a = 600.4(2), b = 1005.1(3), c = 1283.9(4) pm , α= 105.79(9), β = 102.63(7), γ = 103.65(3)°. Each cadmium atom is bonded to one hexamethylenetetramine ligand, one water molecule, and, via the N atoms, to two NCS groups, which act as bridging ligands and form bonds, via the S atoms, to adjacent cadmium atoms. Thus a polymeric chain structure is formed. There is an other water molecule present per formula unit, which is not coordinated to cadmium but is located in channels between the chains. Between the oxygen atoms of this water molecule and the oxygen atom of the coordination water molecule, as well as the nitrogen atom of the hexamethylenentetramine ligand, a system of hydrogen bonds is formed. The coordination of the cadmium atoms is approximately octahedral.
Propargyl-, Allenyl- und Alkinyl-Phosphane; Synthese, Reaktivität, Isomerisierung/ Propargyl-, Allenyl- and Alkynyl-Phosphanes; Synthesis, Reactivity, Isomerization
Authors: Lang Heinrich , Lay Uwe , Leise Michael , Zsolnai Laszlo
Published: March 2015

The synthesis and reactivity of non-coordinated and coordinated propargyl phosphanes are discussed. The isomerization of the propargyl unit in (R)P(Cl)(CH2C ≡ CH ) (3) (R = 2,4,6-tBu3-C6H2O) in the presence of NEt3 yields the allenyl substituted p roduct (R)P(Cl)(CH = C = CH2) (4). However, in the presence of HNEt2 the dimethylenecyclobutane 7 is formed.

Different synthetic pathways for the preparation of LnMP(Ph)m(CH2C ≡ CH)3-m complexes (m = 2: LnM = (η5-C5H5)(CO)2Mn: 10a; LnM = (CO)5Cr: 10b; m = 1: LnM = (η5-C5H5)(CO)2Mn: 13a; LnM = (η5-C 5H4Me)(CO)2Mn: 13b) are described. The synthesis o f the alkynyl substituted phosphane compounds LnMP(Ph)m(C ≡ CR )3-m (m = 2: R = Ph, LnM = (η5-C5H5)(C O )2Mn: 20a; LnM = (CO )5 Cr: 20b; R nBu, LnM = (CO)5 Cr: 20c; m = 1: R = Ph, LnM = (η5-C5H5)(CO)2Mn: 22) was also possible. The reaction of

(η5-C5H4Me)(CO)2,MnPPh (CH2C ≡CH)2 (13 b) with Co2(CO)8 affords in high yields (η5-C5H4Me)(CO)2MnPPh[(η2 -CH2C ≡ CH )Co2(CO )6]2 (15).

All new com pounds have been characterized by analytical and spectroscopic data (IR , 1H -, 13C {1H }-, 31P { 1H } -NMR , MS) and (η5-C5H5)(CO)2MnP(Ph)(CH2C ≡ CH)2 (13a) by X -ray analysis.
[μ-Bis(dialkylphosphino)alkane]-bis[pentacarbonylmetal(0)] Complexes of the Group 6 B Elements: Synthesis and Spectroscopic Study
Authors: Özer Zahide , Özkar Saim
Published: March 2015

[μ-Bis(dialkylphosphino)alkane]-bis[pentacarbonylmetal(0)] complexes (CO)5MR2P(CH2)nPR2M(CO)5, (M: Cr, Mo, W; n: 1, 2, 3; R: CH3, C2H5, C6H5) were synthesized from the reaction of M(CO)5(CH3CN) with the appropriate ligand and characterized by means of IR and NMR (1H , 13C, 31P) spectroscopy. Spectral data indicate that the complexes contain two identical M(CO)5 moieties linked to each other by the R2P(CH2)nPR2 ligand. Each metal atom has a pseudo-octahedral arrangement of the five CO ligands and one phosphorus atom .
The Ternary Uranium Transition Metal Phosphides UV5P3, UCr5P3, and UMn5P3
Authors: Jeitschko Wolfgang , Brink Reinhold , Pollmeier Peter G.
Published: March 2015

The title compounds were prepared from prereacted samples of the elemental components by arc-melting. UCr5P3 was also obtained from a tin flux. UV5P3 and UCr5P3 crystallize with a new structure type, which was determined from X -ray data of a twinned crystal of UCr5P3 :P21/m, a = 959.1(2), b = 370.95(6), c = 696.7(1) pm , β = 100.05(3)°, Z = 2, R = 0.030 for 827 structure factors and 29 variable parameters. UMn5P3 is isotypic with YCo5P3. The structure was refined to a residual of R = 0.054 for 455 structure factors and 28 variables. UCr5P3 has a relatively high, almost temperature independent paramagnetic susceptibility as is frequently observed for metallic uranium compounds. The crystal structures of these phosphides are discussed together with those of other phosphides and silicides of similar composition.