bluuebunny/crossref_metadata_2025 huggingface dataset:
Cp2TiIV-Komplexe mit Oximatoliganden / Cp2TiIV Complexes with Oximato Ligands
Authors: Thewalt Ulf , Friedrich Reinhard
Published: March 2015

The reaction of Cp2TiCl2 with oximes in the two phase system (CHCl3, Cp2TiCl2)/(H2O, NaOH, oxime) leads to ionic complexes of the type [Cp2TiIV(H2O)(oximato)]+X-. Several complexes of this type were prepared. They are surprisingly stable against air and water. The following compounds are described in detail: [Cp2Ti(H2O)(ONC6H10)]NO3 (8) containing a cyclohexanoneoximato ligand, and two complexes with 1,4-cyclohexanedionedioximato ligands, namely the mononuclear complex [Cp2Ti(H2O)(ONC6H8NOH)]Cl · H2O (9) and the dinuclear complex [Cp2Ti(H2O)(ONC6H8NO)(H2O)TiCp2](NO3)2 · 4H2O (10). X-ray structure determinations show, that the ON fragment of the oximato ligand acts as side-on bonded three-electron donating ligand. The Ti atom thus has an 18-electron configuration.
Dialkylaminosubstituierte Phosphiniminophosphonium-Organofluorphosphate und Mono- bzw. Dichlorphosphazene / Dialkylamino Substituted Phosphine Iminophosphonium Organofluorophosphates and Mono- and Dichlorophosphazenes
Authors: Bartsch Rainer , Stelzer Othmar , Schmutzler Reinhard
Published: March 2015

The reaction of N-trimethylsilylphosphine imines, Me3SiN=PR1R2R3, and Me3SiN=P(R1R2)—N=PR1R2R3 (R1, R2, R3 = hydrocarbon or NR, groups) with the fluorophosphoranes PhPF4 and Ph2PF3 and with phosphorus trichloride has furnished phosphine iminophosphonium organofluorophosphates, involving the anions [PhPF5]- or [Ph2PF4]-, and mono- or dichlorophosphino diphosphazenes, respectively. The characterization of these compounds by 1H, 19F and 31P NMR spectroscopy is described.
Diisophorone and Related Compounds, Part 29. 3-Aminodiisophorane Derivatives
Authors: Kurzer Frederick , Patel Jayantilal N.
Published: March 2015

3-Aminodiisophor-2(7)-en-1-ol and homologues are obtained from the readily accessible 3-ketones by reduction of their respective ketoximes, and are characterized as suitable derivatives. The 3-(ω-phenylthioureido) compound undergoes cyclodehydration to a substituted 8,11a-methanocycloocta[d,e][3.1]benzthiazine. The structures of the individual compounds are correlated with their assigned 13C NMR spectra.
Über Dimethylhaloniumsalze – CH3ClCH3
+MF6-, CH3BrCH3
+MF6-, CH3ICH3
+MF6
- – und Dimethylmethylendiiodoniumsalze CH3ICH2ICH3
2+(MF6-)2 (M = As, Sb) / On Dimethylhalonium Salts – CH3ClCH3
+MF6-, CH3BrCH3
+MF6-, CH3ICH3
+MF6
- – and Dimethylmethylendiiodonium Salts CH3ICH2ICH3
2+(MF6-)2 (M = As, Sb)
Authors: Minkwitz Rolf , Gerhard Volker
Published: March 2015

The dimethylhalonium salts (CH3)2X+A- (X = Cl, Br, I; A- = AsF6-, SbF6
-, Sb2F11
-) are synthesized by methylation of the corresponding methylhalides CH3X or dihalomethanes CH2Cl2 and CH2Br2 in the system SO2/CH3F/MF5. The analogous reaction of CH2I2 results in the formation of dimethylmethylendiiodonium hexafluorometallates CH3ICH2ICH3
2+(MF6
-)2 (M = As, Sb). The salts are characterized by Raman-, IR- and NMR-spectroscopy.
Einfache Synthese von 1,2,4,3,5-Trithiadiborolan aus B2H6 und Rohsulfan. Monohydroborierung von Alkinen mit H2B2S3 / Simple Synthesis of 1,2,4,3,5-Trithiadiborolane from B2H6 and Crude Sulphane. Monohydroboration of Alkynes with H2B2S3
Authors: Binder Herbert , Ehmann Wolfgang , Dermentzis Konstantinos
Published: March 2015

B2H6 has been shown to react with H2S2, H2S3 or crude sulphane oil in toluene to form selectively 1,2,4,3,5-trithiadiborolane. The reaction of crude sulphane has been utilized to achieve a convenient synthesis of toluene solutions of H2B2S3 which are stable on standing at 0 °C. A mechanism for the sulphur chain degradation in polysulphanes is proposed. Monohydroboration of alkynes proceeds by cis addition from the less hindered side of the triple bond. Both hydrogen atoms of H2B2S3 react with 1- or 2-alkynes thus leading to 3,5-dialkenyl-1,2,4,3,5-trithiadiborolane derivatives, respectively.
Schwingungsspektren und Normalkoordinatenanalyse der heteroleptischen Halogenohexaborate B6XnY6-n
2-, n = 1-5; Χ ≠ Υ = Cl, Br, I / Vibrational Spectra and Normal Coordinate Analysis of the Heteroleptic Halogenohexaborates B6XnY6-n
2-, n = 1— 5; Χ ≠ Y = Cl, Br, I
Authors: Thesing J. , Stallbaum M. , Preetz W.
Published: March 2015

Normal coordinate analyses for the 24 mixed halogenohexaborates B6XnY6-n
2-, n = 1—5, Χ ≠ Y = Cl, Br, I, including the pairs of geometric isomers for n = 2, 3, 4 have been performed, based on a general valence force field. Using the bond lengths and force constants for the homoleptic species B6X6
2-, which with respect to the B6 cage are weighted standardized, the calculated frequencies are in good agreement with observed IR and Raman bands. The boronhalogen stretching vibrations for symmetric molecular axes correspond with the Ra(IR) bands of the homoleptic compounds: ClB6Cl 327 (515), BrB6Br 207 (430), IB6I 152 (394) cm-1. As a characteristic feature the mixed halogeno clusters exhibit bands with nearly averaged frequencies from asymmetrical axes: ClB6Br 261 (487), ClB6I 227 (473), BrB6I 178 (409) cm-1. This complete vibrational coupling is confirmed by properly balanced potential energy distribution on BX and BY bonds. There is a slight influence of the different substituents on the internal modes of the B6 cage (pseudo-Oh), observed in the sequence A1g>T1u> Eg>T2g in the region 1220-740 cm-1. The bands are shifted about 100 cm-1 with increasing mass of halogen, broadened by boron isotopomers (max. 60 cm-1), and degenerate vibrations are split by lowered point and site symmetry up to 100 cm-1.
Darstellung und Kristallstrukturen von Phenyliodoantimonaten(III). Strukturkorrelation für Halogenoantimonate(III) / Preparation and Crystal Structures of Phenyliodoantimonates(III). Structural Correlation for Haloantimonates(III)
Authors: Sheldrick W. S. , Martin C.
Published: March 2015

The phenyliodoantimonates(III) [Et4N][Ph2SbI2] (1), [Et4N]2[Ph2Sb2I6] (2) and [Hpy]3[Ph2Sb2I7] (3) have been prepared and their structures established by X-ray structural analysis. The anion [Ph2SbI2]⁻ displays a ψ-trigonal bipyramidal structure with axial Sb–I distances of 2.925(1) and 3.109(1) A. In the dimeric anions [Ph2Sb2I6]2- and [Ph2Sb2I7]3- the antimony atoms exhibit ψ-octahedral geometries. As observed for [Ph2SbI2]⁻, terminal Sb–I bonds in trans-position to one another display significantly different lengths. The anion [Ph2Sb2I7]3- displays Ci- symmetry with a bridging iodine atom at the crystallographic centre of symmetry. Long Sb—I distances of 3.404(1) A are observed to this atom. A structural correlation of opposite Sb–X distances (X = Cl, Br, I) in linear three centre X–Sb ··· X interactions is presented. The sum of the bond valences in iodoantimonates(III) is a minimum for symmetrical I–Sb–I three centre bonds, reflecting thereby the antibonding influence of the Sb 5 s-orbital. This influence is considerably smaller for bromoantimonates(III) and may be effectively neglected for chloroantimonates(III).
Pentasulfid-Chelate mit überbrücktem Vanadocen-Gerüst / Pentasulfide Chelates with Bridged Vanadocene System
Authors: Klouras Nikolaos
Published: March 2015

The [1]vanadocenophanes Me2E(C5H4)2VCl2 (1c) (E = Si, Ge) have been prepared by the metallation of the bis(cyclopentadienyl) compounds Me2E(h1-C5H5)2 (1a) with butyllithium and subsequent reaction with vanadium(IV) chloride. The complexes lc react with an excess of (NH4)2S5 to give Me2E(C5H4)2VS5 (1d), the first pentasulfide chelate with a bridged vanadocene system.
Notizen: Kieselsäureester als Komplexliganden / Silicic Acid Esters as Complexing Ligands
Authors: Marsmann Heinrich C. , Seifert Meinolf
Published: March 2015

The distribution of alkali ions between an aqueous and an organic phase (CH2Cl2) in the presence of the cyclic silicic acid esters [OSi(OR)2]n (n = 3,4, R = CH3, Si(CH3)3) was determined. The silicic acid esters are about as effective as crown ethers in their extracting power.
Notizen: Zur Reaktion von [{Cp(Ph3P)Ni}SnCl3] mit Bis(trimethylsilyl)selenan. Die Kristallstruktur von [Cp4(Ph3P)3Ni5Sn6Se9] / Reaction of [{Cp(Ph3P)Ni}SnCl3] with Bis(trimethylsilyl)selenane. The Crystal Structure of [Cp4(Ph3P)3Ni5Sn6Se9]
Authors: Merzweiler Kurt , Weisse Laurent
Published: March 2015

[{Cp(Ph3P)Ni}SnCl3] reacts with (Me3Si)2Se in toluene as solvent to form the compound [Cp4(Ph3P)3Ni5Sn6Se9] (4). The structure of 4 was determined by X-ray diffraction. 4 contains a polycyclic Sn6Se9-cage which encloses a central CpNi2 unit.
Additionen an die Si=N-Doppelbindung – Kristallstruktur eines (SiNCO)-Vierringes / Additions to the Si=N-Double Bond - Crystal Structure of a (SiNCO)-Four Membered Ring
Authors: Vollbrecht Susanne , Klingebiel Uwe , Schmidt-Bäse Dieter
Published: March 2015

In the reaction with benzophenone and phenylaldehyde lithiated aminofluorosilanes behave like iminosilanes. Four membered rings are formed in (2+2) cycloadditions. The oxaazasilacyclobutane ((CMe3)2Si—NCMe3—C6H5CH—O—) was purified by destillation. Single crystals were obtained by recrystallization from hexane. The thermal cleavage of the (SiNCO)-rings leads to carboimines and cyclosiloxanes. The lithium derivate of di-tert-butylfluorosilyl-2.6-diisopropylphenylamine reacts with 2-methyl-propenal-2 in two competing ways. In a (2+4) cycloaddition an 1-oxa-3-aza-2-sila-5-cyclohexene is formed, and in a (2+2) cycloaddition 2-methyl-2-propenyl-N-(2.6-diisopropylphenyl)imine is generated via an (SiNCO)-ring intermediate.
Synthese von Stickstoff- und Chlor-verbrückten Indiumorganylen. Die Kristallstrukturen von [Mes(Cl)InN(SiMe3)2]2 und {i-Pr2In[N(H)t-Bu]2In(Cl)i-Pr} / Synthesis of Nitrogen- and Chloro-Bridged Organoindium Compounds. The Crystal Structures of [Mes(Cl)InN(SiMe3)2]2 and {i-Pr2In[N(H)t-Bu]2In(Cl)i-Pr}
Authors: Neumüller Bernhard
Published: March 2015

[(PhCH2)2InN(H)t-Bu]2 (3) and [PhCH2(Cl)InN(SiMe3)2]2 (4) have been prepared by the reaction of (PhCH2)2InCl with LiN(H)t-Bu and of PhCH2InCl2 with NaN(SiMe3)2, respectively. 3 could be isolated in two isomers, while 4 forms only one chloro-bridged isomer in solution and in the solid state. The possibility of a chloro-bridged alkyl(aryl)chloroindium amide is also realized in [Mes(Cl)InN(SiMe3)2]2 (2), as shown by X-ray analysis. The reaction of a 1:1-mixture of i-Pr2InCl/i-PrInCl2 with LiN(H)t-Bu leads to all three possible compounds: [i-Pr(Cl)InN(H)t-Bu]2 (1), {i-Pr2In[N(H)t-Bu]2In(Cl)i-Pr} (5), and [i-Pr2InN(H)t-Bu]2 (6). Two isomers of the new compound 5 are detectable in solution. The crystal structure has been determined for the less sterically hindered isomer 5a, which forms hydrogen-bridged (Cl-H-N-bridge) infinite chains along the c-axis.
Synthese und Struktur aminosubstituierter Tetraphosphetane / Synthesis and Structure of Amino-Substituted Tetraphosphetanes
Authors: Appel R. , Gudat D. , Niecke E. , Nieger M. , Porz C. , Westermann H.
Published: March 2015

A number of aminotetraphosphetanes could be obtained by reductive dehalogenation of dichlorophosphines with magnesium as well as by elimination of chlorotrimethylsilane from vicinal chlorosily-functionalized biphosphines and from [2+2]-cyclodimerization of aminodiphosphenes, respectively. The molecular structures of several tetraphosphetanes are reported and discussed. The torsion-angle of the four-membered rings varies from 22.5° to 45.7°, depending on the size and electronegativity of the exocyclic ligands.
Modellsysteme für die Gallium-Extraktion, I. Struktur und Moleküldynamik von Aluminium- und Galliumtris(oxinaten) / Model Systems for Gallium Extraction, I. Structure and Molecular Dynamics of Aluminium and Gallium Tris(oxinates)
Authors: Schmidbaur Hubert , Lettenbauer Josef , Wilkinson Dallas L. , Müller Gerhard , Kumberger Otto
Published: March 2015

Tris(oxinato) complexes of aluminium(III) and gallium(III) have been prepared from 8-oxyquinoline (OxH) and its six C-methylated derivatives from aqueous solutions of the metal chlorides or nitrates and an ammonium acetate buffer. Crystalline monohydrates or (upon precipitation with methanol) mono-methanol adducts are obtained. Single crystal X-ray diffraction studies reveal a meridional tris(chelate) structure for the two (isomorphous) tris(oxinates) Al(Ox)3 · MeOH and Ga(Ox)3 · MeOH with distinct differences in the individual dimensions. (The MeOH molecules form strong hydrogen bonds with one of the oxygen atoms.) For these species and those of the substituted ligands 3-MeOx, 4-MeOx, 5-MeOx, 6-MeOx, and 7-MeOx a similar meridional structure was confirmed by low temperature 1H NMR spectroscopy, which showed three inequivalent sets of ligands in each case. The collaps of these signals at elevated temperatures indicates a ligand-equilibrating process, with the mechanism probably comprising a dissociation of a pyridine function from the metal, to give a fluctional pentacoordinate species with free rotation about the intact M—O bond, and an M—N recombination at a random octahedral site. For the 2-MeOx ligands, however, the facial structure is preferred at lower temperature, but with the meridional isomer present as a component of an equilibrium. This indicates the strong steric influence of substituents in 2-position of the 8-oxy-quinoline.
Two New Flavones from Inula grantioides
Authors: Ahmad Viqar Uddin , Ismail Nargis
Published: March 2015

Two new flavones grantionin 1 and grantioidinin 2 have been isolated from Inula grantioides and their structures were determined as 7-hydroxy-6,3′,5′-trimethoxy flavone 1 and 5-hydroxy-3,6,7,8,2′,5′-hexamethoxy flavone 2 along with a known dinorsequiterpene pluchidione 3.
Synthese und Kristallstruktur des Amido-Palladats (PPh4)2[Pd2Cl4(NH2)2] · CH2Cl2 und des Benzamidin-Palladats PPh4{ [Ph– C(NH2)(NH)]PdCl3} · CH3CN / Synthesis and Crystal Structure of the Amido Palladate (PPh4)2[Pd2Cl4(NH2)2] · CH2Cl2 and of the Benzamidine Palladate PPh4{[Ph—C(NH2)(NH)]PdCl3} · CH3CN
Authors: Arnim Henning von , Massa Werner , Zinn Alfred , Dehnicke Kurt
Published: March 2015

Orange crystals of (PPh4)2[Pd2Cl4(NH2)2] have been prepared by the reaction of (PPh4)2[Pd2Cl6] with N,N,N′-tris(trimethylsilyl)benzamidine in boiling acetonitrile in the presence of water, and orange brown crystals of PPh4{[Ph—C(NH2)(NH)]PdCl3} by the reaction of the amidinato complex PPh4[Ph—C(NSiMe3)2PdCl2] with HCl gas in acetonitrile solution. The complexes were characterized by IR spectroscopy as well as by X-ray structure determinations.

(PPh4)2[Pd2Cl4(NH2)2] · CH2Cl2: Space group PĪ, Z = 1, 2784 observed unique reflections, R = 0.043. Lattice dimensions at —60 °C: a = 1053.3(4), b = 1081.1(4), c = 1249.2(4) pm, α = 102.90(2)°, β = 110.44(2)°, γ = 102.23(2)°. The compound consists of PPh4
+ ions and centrosymmetric anions [Pd2Cl4(NH2)2]2- with bridging chlorine atoms and terminal amido groups.

PPh4{[Ph—C(NH2)(NH)]PdCl3} -CH3CN: Space group C2/c, Z = 8, 1183 observed unique reflections, R = 0.033. Lattice dimensions at —60 °C: a = 3106.7(6), b = 1059.0(1), c = 1818.0(4) pm, β = 90.98(2)°. The compound consists of PPh4
+ ions, [Ph—C(NH2)(NH)PdCl3]-ions, and included CH3CN molecules. In the anion the benzamidine ligand is bound via the nitrogen atom of the imido group.
Synthese und Kristallstruktur von (PPh4)2Te4 / Synthesis and Crystal Structure of (PPh4)2Te4
Authors: Wolkers Hans , Schreiner Bernhard , Staffel Rüdiger , Müller Ulrich , Dehnicke Kurt
Published: March 2015

(PPh4)2Te4 has been prepared by the reaction of Na2Te3 with PPh4Cl in DMF solution in the presence of MnCl2 or FeCl2. The compound forms dark red crystals, which were characterized by IR spectroscopy as well as by an X-ray crystal structure determination (6109 observed independent reflections, R = 0.030). Crystal data: triclinic, space group PĪ, Z = 2, a = 1046.7(2), b = 1130.1(2), c = 1967.8(4) pm, α = 93.63(3), β = 90.43(3), γ = 108.89(3)° at —60 °C. The cations are grouped in pairs (PPh4
+)2 around inversion centres, each pair being surrounded by eight Te4
2- ions, arranged as in the CsCl type lattice. The chain-like Te4
2- ions have no close contacts with one another.
Synthese und Strukturanalyse des gemischten Alkalimetallorthonitrats Na3K3(NO4)2 / Synthesis and X-Ray Structure Determination of the Mixed Alkali Metal Orthonitrate Na3K3(NO4)2
Authors: Bremm Thomas , Jansen Martin
Published: March 2015

The title compound has been characterized by X-ray powder and single crystal diffraction: Pbcn; a = 7.296(1), b = 15.997(4), c = 7.016(1) Å; Z = 4; 1514 diffractometer data, R = 0.04, Rw = 0.03. The vibrational spectra are compatible with a tetrahedral geometry of the anion.
Elektronentransfer und Ionenpaar-Bildung, 20 / Electron Transfer and Ion Pairing, 20
Authors: Bock H. , Jaculi D.
Published: March 2015

Cyclovoltammetric measurements of solutions containing the rather basic tetra-(2′-pyridyl)pyrazine allow to detect even traces of water and thus can be used as a touchstone for aprotic (cH⊕ < 1 ppm) conditions. On exchange of the “innocent” tetrabutylammonium R4N⊕ as supporting electrolyte cation by “interactive” ones such as Li⊕) or Na⊕, considerable changes in the reduction potentials are observed due to ion pair formation.
Synthese und Eigenschaften von Lipoaminosäuren und Lipodipeptiden des Ornithins / Synthesis and Properties of Lipo Amino Acids and Lipodipeptides of Ornithine
Authors: Kellner Gerhard , Liefländer Manfred
Published: March 2015

Lipo amino acids and α- as well as δ-connected lipodipeptides of ornithine were synthesized. The lipid portion was introduced to the amino group by acylating with hexadecanoyl chloride and to the carboxylic group by amidating with hexadecylamine or octadecylamine, respectively. Due to their amphiphilic properties these compounds were measured in a LANGMUIR-trough and thus their ability to form monomolecular films was examined. Dates from the surface pressure - area isotherms are listed in the following composition.
Chemistry of Phosphorus Ylides, 11
Authors: Soliman Fouad M. , Said Medhat M.
Published: March 2015

The reaction of 1-hydroxyxanthenone (1) and hydroxyquinoline (10, 13) Mannich bases with the reactive phosphacumulated ylides (2), represents a new way for the synthesis of the pyranones and pyranthiones (5, 11, 14). On the other hand, the stabilized phosphorus ylides (6) affect the transylidation of the Mannich base (1) to the corresponding phosphoranylidenes (9). The structure of the resulting new compounds has been confirmed through elemental analysis and spectroscopic results (IR, 1H, 31P NMR and MS).
Notizen: Preparation of Some Bis(alkylthio)-bis(alkylseleno)tetrathiafulvalenes
Authors: Papavassiliou G. C. , Kakoussis V. C. , Lagouvardos D. J.
Published: March 2015

Methylenedithioethylenediselenotetrathiafulvalene, methylenedithiotrimethylenediselenotetrathiafulvalene, ethylenedithiomethylenediselenotetrathiafulvalene, trimethylenedithiomethylenediselenotetrathiafulvalene, vinylenedithioethylenediselenotetrathiafulvalene, vinylenedithiotrimethylenediselenotetrathiafulvalene, ethylenediselenodioctadecylthiotetrathiafulvalene, trimethylenediselenodioctadecylthiotetrathiafulvalene, ethylenedithiodioctadecylselenotetrathiafulvalene, trimethylenedithiodioctadecylselenotetrathiafulvalene and ethylenedithioethylenediselenotetrathiafulvalene have been prepared and characterized analytically and spectroscopically.
Extrem asymmetrisch gebundene Wassermoleküle-Kristallstrukturen von Sr(OH)Cl · 4 H2O, Sr(OH)Br · 4 H2O und Ba(OH)I·4 H2O / Extremely Asymmetrically Bound Water Molecules-Crystal Structures of Sr(OH)Cl · 4 H2O, Sr(OH)Br · 4 H2O, and Ba(OH)I·4 H2O
Authors: Kellersohn Thomas , Beckenkamp Konrad , Lutz Heinz Dieter
Published: March 2015

The crystal structures of isotypic Sr(OH)Cl ·4 H2O, Sr(OH)Br·4 H2O, and Ba(OH)I·4 H2O are reported. The title compounds crystallize in a hitherto unknown structure type, space group PĪ, Z = 2. The final R values obtained are 0.0261, 0.069, and 0.062, respectively. The coordination of the metal ions is monocapped square antiprismatic with 7 H2O, 1 OH- and 1 halide ion. The halide ions separate metal/water/hydroxide layers. Each of the four crystallographically different water molecules serves as donor for one very strong and one very weak hydrogen bond and, hence, is extremely asymmetrically bound. Owing to this strong distortion, the largest one known so far, the OH stretching vibrations of the H2O molecules are intramolecularly decoupled as shown from vibrational spectra. The enthalpies of dehydration obtained from differential scanning calorimetry are reported.
Metallkomplexe mit funktionalisierten Schwefelliganden, I / Metal Complexes of Functionalized Sulphur Containing Ligands, I
Authors: Weigand Wolfgang
Published: March 2015

Complexes of the types cis-L2PtCl2 (L = PPh3, 1/2 dppe) and cpRu(PPh3)2Cl react with 1-alkyne-1-thiolates to give the products trans-(Ph3P)2Pt(S–C≡C–Ph)2 (5), dppePt(S–C≡C–Ph)2 (6) and CpRu(PPh3)2(S–C≡C–Ph) (7), respectively. CpRu(PPh3)(CO)(S–C≡C–Ph) (8) is formed by reaction of 7 in an atmosphere of CO. The 2-propene-1-thiolato complexes dppePt(S–CH2–CH = CH2)2 (9), CpFe(CO)2(S–CH2–CH=CH2) (12) and CpFe(PPh3)(CO)(S–CH2–CH=CH2) (13) are obtained from dppePtCl2, CpFe(CO)2I, CpFe(PPh3)(CO)I and lithium or sodium 2-propene-1-thiolate. The complexes are characterized by IR and 1H,13C and 31P NMR spectroscopy.
Neue mehrkernige Pd-Komplexe mit S, Se und PPh3 als Liganden. Die Kristallstrukturen von [Pd5Se4Cl2(PPh3)6], [Pd4NiS4Cl2(PPh3)6], [Pd5Se5(PPh3)5], [Pd6Se4Cl4(PPh3)6], [Pd7Se6(SeH)Cl(PPh3)7], [Pd8Se8(PPh3)8] und [Pd8Se8Cl(PPh3)8] + [CpCrCl3]- / New Multinuclear Pd Complexes with S, Se and PPh3 as Ligands. The Crystal Structures of [Pd5Se4Cl2(PPh3)6], [Pd4NiS4Cl2(PPh3)6], [Pd5Se5(PPh3)5], [Pd6Se4Cl4(PPh3)6], [Pd7Se6(SeH)Cl(PPh3)7], [Pd8Se8(PPh3)8] and [Pd8Se8Cl(PPh3)8]+[CpCrCl3]-
Authors: Fenske Dieter , Fleischer Holm , Krautscheid Harald , Magull Jörg , Oliver Christopher , Weisgerber Sabine
Published: March 2015

[PdCl2(PPh3)2] reacts with Se(SiMe3)2 to form a mixture of multinuclear Pd complexes, [Pd3Se2(SeSiMe3)2(PPh3)4] (1), [Pd5Se5(PPh3)5] (2) and [Pd8Se8(PPh3)8] (3). 1 can be used as starting material for the synthesis of further Pd clusters. Reactions of 1 with [CpCrCl2(THF)], [PdCl2(PPh3)2] and [NiCl2(PPh3)2] lead to the formation of [Pd6Se4Cl4(PPh3)6] (4), [Pd8Se8Cl(PPh3)8]+[CpCrCl3]- (5), [Pd5Se4Cl2(PPh3)6] (6) and [Pd7Se6(SeH)Cl(PPh3)7] (7). The complexes [Pd6Se4(SeH)2Cl2(PPh3)6] and [Pd6Se4(SeH)4(PPh3)6] have structures similar to 4, and are formed by reaction of [PdCl2(NBD)] or [PdCl(COD)]2(BF4)2 with PPh3 and Se(SiMe3)2.

Reaction of [(C3H5)PdCl]2 with [NiCl2(PPh3)2] and S(SiMe3)2 leads to the formation of the heterometal cluster [Pd4NiS4Cl2(PPh3)6] (8).

The molecular structures of 2-8 show quite clearly that these compounds may be considered as intermediates on the route towards multinuclear Pd complexes.
Halogenierung und Acyloxylierung von N-Cyclohex-2-en-1-on-3-yl-aminosäuren / Halogenation and Acyloxylation of N-Cyclohex-2-en-1-on-3-yl-amino Acids
Authors: Habermehl Gerhard G. , Wippermann Irene , Krebs Hans Chr. , Dieck Susanne tom
Published: March 2015

Secondary enaminones 2 are easily halogenated to yield the so far unknown halogenides 3,4 and 5. Acyloxylation of enaminones 2 by dibenzoylperoxide leads to benzoyloxylated substances 13, which also have not been described jet. Bisacylated products could not be traced. Only the rearranged compounds 14 could be isolated. 14b showed cytotoxic activity.
On the Chemistry of Ingenol, IV [1]
Authors: Bagavathi R. , Sorg Bernd , Hecker Erich
Published: March 2015

A simple and fast procedure was worked out to prepare from the commercially available seeds of Euphorbia lathyris L. substantial amounts of the polyfunctional tetracyclic diterpene ingenol (la). Ingenol-3,4:5,20-diacetonide (1d) was treated with five different bases at two different temperatures to achieve epimerization to 8-epiingenol. In any case unchanged 1 d was obtained. By reduction of ingenol-3,4: 5,20-diacetonide (1d) with sodium in ether/2-propanol (9 R)-9-deoxo-9-hydroxyingenol-3,4:5,20-diacetonide (2b) was obtained and converted to the corresponding 5,20-monoacetonide 2e. Reduction of ingenol-5,20-acetonide (le) with LiAlH4 in tetrahydrofuran furnished the epimeric (9 S)-9-deoxo-9-hydroxyingenol-5,20-acetonide (3c).The (9 R)-monoacetonide 2e was used to prepare the 3-tetradecanoate 2c of (9 R)-9-deoxo-9-hydroxyingenol (2a). From the (9 S)-monoacetonide 3 c four 3-esters [butyrate (3d), tetradecanoate (3e), eicosanoate (3f), benzoate (3g)] of (9S)-9-deoxo-9-hydroxyingenol (3 a) were synthesized. The 3,4 : 5,20-diacetonides of 2a and 3a, i.e. 2b/3b were used to provide the 9-hexadecanoates 2 f and 3j. The irritant activities of the 3-esters of the (9 S)-series depend strongly on the nature of the acyl group, thus furnishing, e. g. the moderately irritant tetradecanoate 3e [compared to corresponding 3-esters lb of ingenol (la)] as well as the highly active benzoate 3g of 3 a. The (9 R)-3-tetradecanoate 2c exhibits comparable activity as its (9 S)-analogue 3e. Thus, the spatial orientation (R or S) of the 9-hydroxy function plays a significant but not a crucial role for irritant activity. Both epimeric (9 R)/(9 S)-hexadecanoates 2f/3j were non-irritant.
27Al-MAS-NMR-Untersuchungen des thermischen Abbaus von NH4Al(SO4)2·12H2O / 27Al-MAS-NMR Studies on the Thermolysis of NH4Al(SO4)2· 12H2O
Authors: Wegner Gerhard , Blumenthal Gert , Müller Dirk , Menz Dirk-Henning , Schmalstieg Antje
Published: March 2015

Products of the thermolysis of NH4Al-alum were prepared under dried air and characterized by X-ray powder diffraction, thermogravimetry, and for the first time by solid-state 27Al-MAS-NMR spectroscopy. It was found, that high resolution NMR spectroscopy is applicable to follow up the thermal decomposition and to indicate even minor structural changes. 27Al-MAS-NMR spectra show peaks with characteristic chemical shifts for octahedral Al-units up to a high stage of thermolysis. During the decomposition of Al2(SO4)3 to γ-Al2O3 we again observed three-peak spectra with the specific signal at ≈ 35 ppm for penta-coordinated Al ions as recently proved for the thermolysis of AlCl3 · 6 H2O.
Darstellung und Kristallstruktur von [(Me3Si)2CH(i-Pr)InCl]2 / Synthesis and Crystal Structure of [(Me3Si)2CH(i-Pr)InCl]2
Authors: Neumüller Bernhard
Published: March 2015

The title compound 1 has been prepared by the reaction of i-PrInCl2 with LiCH(SiMe3)2 in diethylether at -30 °C. The colorless substance 1 was characterized by NMR, IR, and RE spectroscopy, as well as by mass spectrometry. 1 is dimer in solution and the solid state and crystallizes in the space group P21/c with the cell parameters a = 1206.4(3) pm, b = 905.7(2) pm, c = 1591.2(5) pm, and β = 101.18(2)°. The unit cell contains two centrosymmetrical dimeric molecules.
Preparation and Vibrational Spectra of Me2Sn(O2PMe2)2, Cl2Sn(O2PMe2)2 and Al(O2PMe2)3
Authors: Shihada Abdel-Fattah , Yousif Hekmat R.
Published: March 2015

Me2Sn(O2PMe2)2 has been prepared from the reaction of Me2PO2H and Me2SnS in benzene, and Al(Ο2ΡΜe2)3 and Cl2Sn(O2PMe2)2 have obtained from the reaction of Me2PO2H with AlCl3 and SnCl4, respectively in CH2Cl2. The vibrational spectra of the compounds were found to be consistent with polymeric structures with hexacoordinated metal atoms.
Übergangsmetallkomplexe mit Schwefelliganden, LXXIII. Diastereospezifische Dichlormethylierung schwefelreicher [RuII(SRR′)(PPh3)′S4]-Komplexe (SRR′ = einzähniger Thioether- oder Thiol-Ligand; ′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, LXXIII. Diastereospecific Dichloromethylation of Sulfur Rich [RuII(SRR′)(PPh3)′S4] Complexes (SRR′ = Monodentate Thioether or Thiol Ligand;′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))
Authors: Sellmann Dieter , Lechner Peter , Knoch Falk , Moll Matthias
Published: March 2015

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.

The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.
Differenzelektronendichte im gefalteten 2 π-aromatischen System eines 1,3-Dihydro-1,3-diborets / Difference Electron Density in a Folded 2π-Aromatic System of a 1,3-Dihydro-1,3-diborete
Authors: Irngartinger Hermann , Hauck Jürgen , Siebert Walter , Hildenbrand Manfred
Published: March 2015

The crystal structure and the X—X difference electron density distribution of 1,3-bis(diisopropylamino)-1,3,dihydro-1,3-diborete (1) has been determined at the temperature of 107 K. Both π-electrons of the folded aromatic four membered ring system (folding angle 47.6°) are uniformly distributed on the four ring bonds with equal lengths (B—C 1.524 A). These bonds are significantly bent.
Über die Reaktion von Wolframhexachlorid mit Se4N2; Kristallstruktur von PPh4[WCl5(NSeCl)] / On the Reaction of Tungsten Hexachloride with Se4N2; Crystal Structure of PPh4[WCl5(NSeCl)]
Authors: Vogler Stefan , Massa Werner , Dehnicke Kurt
Published: March 2015

The reaction of tungsten hexachloride with Se4N2 leads to [WCl4(NSeCl)]2, which reacts with pyridine to form [WCl4(NSeCl)Py], and with tetraphenylphosphonium chloride to form PPh4[WCl5(NSeCl)], which was characterized by an X-ray structure determination. Space group P21, Z = 2, 1657 observed unique reflections, R = 0.074, wR = 0.061. Lattice dimensions at —80 C: a = 710.7(1), b = 2217.9(4), c = 953.6(2) pm; β = 111.93(3) . The [WCl5(NSeCl)]- ion possesses an almost linear WNSe group with bond lengths WN = 188 pm, corresponding to a double bond, and NSe = 200 pm.
57Fe-15N Spin-Spin Coupling at Natural Abundance of the Isotopes in Binuclear Complexes Fe2(CO)6(μ-RNS) Containing a Sulfimide Bridge
Authors: Wrackmeyer Bernd , Kupče Ēriks , Distler Berthold , Dirnberger Klaus , Herberhold Max
Published: March 2015

Complexes of the type Fe2(CO)6(μ-RNS) [R = H (la), tBu (lb), SiMe3 (lc), Si'BuMe2 (1d), SnMe3 (le)] have been studied by multinuclear magnetic resonance (1H13C, 14C, 14N, 15N, 17O, 29Si, 119Sn) with emphasis on natural abundance 15N NMR measurements. By application of various polarization transfer techniques 1J(57Fe15N) (6.1 Hz) in la has been determined for the first time, together with the isotope-induced shift 1Δ34/32S (-36 ppb). Compound ld has been prepared via the reaction between Me2
tBuSiCl and Fe2(CO)6(μ-NaNS) (lf), available from la and sodium.
Tetramethyld-η2-vinyldisiloxan(triphenylphosphan)platin(0) / Tetramethyldi-η2-vinyldisiloxane(triphenylphosphine)platinum(0)
Authors: Beuter Georg , Heyke Olga , Lorenz Ingo-Peter
Published: March 2015

The reaction of (Ph3P)2PtC2H4 with the divinyldisiloxane (CH2=CHSiMe2)2O in toluene yields Pt{(η2-H2C=CHSiMe2)2O}PPh3, which has been characterized by IR, 1H, 13C, 31P NMR and MS spectra. The crystal structure was determined by X-ray diffraction: space group C2/c, Z = 16, a = 5534.2(9), b = 842.6(2), c = 2383.1(2) pm, β = 103.73(1)°, R/Rw = 0.047/0.052. It shows a three-coordinate platinum atom with one phosphine and one sym-tetramethyldivinyldisiloxane ligand acting as a chelating bidentate η/2-ligand to give a chair conformation of the six-membered PtC2Si2O-ring system.
Novel Synthesis of 4-Aroyl-6-phenylpyridazin-3(2 H)-ones
Authors: Ismail M. F. , Sayed F. S. , Emara S. A. , Shindy A. A.
Published: March 2015

4-Aroyl-6-phenylpyridazin-3(2 H)-ones (4a—c) were synthesized by the oxidation of the corresponding 4-arylmethyl-6-phenylpyridazin-3(2H)-ones (3a—c) using sodium dichromate in glacial acetic acid. The reactions of 4a—c with hydrazine hydrate and hydroxylamine hydrochloride proceeded smoothly to give the corresponding hydrazones (5) and oxime (6). 4a—c reacted with dimethyl sulphate to give 4-aroyl-2-methyl-6-phenylpyridazin-3(2 H)-ones (7a—c), respectively while their reaction with phosphorus oxychloride gave 4-aroyl-3-chloro-6-phenylpyridazines (9a—c), respectively.
Notizen: 5,6-Ethylenediseleno-1,3-dithiolo[4,5-b][1,4]-dithiin-2-thione as Starting Material for the Preparation of New Tetrathiafulvalenes
Authors: Papavassiliou G. C. , Lagouvardos D. J. , Kakoussis V. C.
Published: March 2015

Starting from 1,3-dithiolo[4,5-b][1,4]dithiin-2-thione, the title thione was prepared by a fourstep sequence (lithiation with lithium diisopropylamide, addition of Se, treatment with ZnCl2 in the presence of n-Bu4NBr, and alkylation with 1,2-dibromoethane). Self-coupling as well as cross-coupling with similar compounds via triethyl phosphite afforded new tetrathiafulvalenes, precursors of conducting salts.
Notizen: Über die Darstellung der Sulfuran-Addukte CF3S(O)F · MF5 (M = As, Sb) und (CF3)2SO · SbF5 [1] / On the Preparation of the Sulfurane Adducts CF3S(O)F · MF5 (M = As, Sb) and (CF3)2SO · SbF5 [1]
Authors: Minkwitz Rolf , Molsbeck Walter
Published: March 2015

The adducts CF3S(O)F · MF5 (M = As, Sb) and (CF3)2SO · SbF5 have been prepared by reaction of the sulfuranes CF3S(O)F and (CF3)2SO with AsF5 and SbF5 in liquid HF, and characterized by Raman and 19F NMR spectroscopy.
Die Kristallstrukturen von Na2CoFeF7 und einer zweiten Modifikation von Na2CuFeF7: Eine weitere Weberit-Variante / The Crystal Structures of Na2CoFeF7 and a Second Modification of Na2CuFeF7: Another Weberite Variant
Authors: Welsch Matthias , Babel Dietrich
Published: March 2015

The monoclinic weberites Na2CoFeF7 (a = 1262.2(10), b = 736.0(4), c = 2451.6(20) pm, β = 99.71(5)°) and a second modification of Na2CuFeF7 (a = 1244.4(2), b = 734.3(1), c = 2467.2(5) pm, β = 99.27(3)°), crystallize isotypically in space group C 2/c, Ζ = 16. The structure is an intermediate type between orthorhombic and trigonal weberites, characterized by pairs ofparallel chains of octahedra [MF4F2/2]3- (M = Co, Cu) which run in turn along [110] and [110]. The average distances are Fe-F = 192 pm in the [FeF63- octahedra of both compounds. Considerable splitting of distances occurs in the [CoF6- octahedra (av. Co-F = 201 pm), and by Jahn-Teller distortion even more in those of [CuFJ4- (av. Cu-F = 199 pm). One of the copper surroundings is (pseudo)tetragonally elongated (av. 209/194 pm), the other exhibits an unusual splitting into three long and three short bonds (av. 204/193 pm) in meridional positions. Some structural relations are discussed.
Ein neuer Zugang zu Tetrathiooxalaten. Die Kristallstruktur von (NEt4)2[C2S4] / A Novel Access to Tetrathiooxalates. Crystal Structure of (NEt4)2[C2S4]
Authors: Bacher Alfred D. , Sens Irina , Müller Ulrich
Published: March 2015

(NEt4)2S5 was prepared from NEt4Cl and Na2S4 in ethanol. Its reaction with boiling acetonitrile yielded tetraethylammonium tetrathiooxalate. (NEt4)2[C2S4] was also obtained by heating (NEt4)2S5 with tetraethylammonium dithioacetate in ethanol. Benzyltriethylammonium tetrathiooxalate, (NEt3Bz)2[C2S4]· 2 toluene, crystallized after NEt3BzCl and Na2S4 were heated in acetonitrile on subsequent addition of toluene. The crystal structure of (NEt4)2[C2S4] was determined by X-ray diffraction (454 independent observed reflexions, R = 0.047). Crystal data: tetragonal, a = 871.2(1) pm, c = 1566.0(3) pm, space group P42/nmc, Z = 2. The [C2S4]2- ion has point symmetry 4m2 (D2d), i.e. the dihedral angle between the two CS2 groups is 90°. The ethyl groups of the NEt4
+ ions are disordered in two orientations.
Synthesis and Properties of Bis-(phenylenedithio)-tetrathiafulvalene (BPhDT-TTF): a New π-Donor for Organic Metals
Authors: Müller Harald , Fritz Heinz P. , Nemetschek Ralf , Hackl Rudolf , Biberacher Werner , Heidmann Claus-Peter
Published: March 2015

The new π-donor bis-(phenylenedithio)-tetrathiafulvalene (5), synthesized via phosphite coupling of 2-oxo-1,3-dithiolo-[4,5b][1,4]-benzodithiin (4), has been prepared in 5 steps starting from 1,2-dimercaptobenzene and chloroacetyl chloride. Spectroscopic and electrochemical data point to a close similarity of 5 and dibenzo-tetrathiafulvalene (DB-TTF). 5 forms a highly conducting radical-cation salt (σRT = 100 S/cm) with AsF6- as counter ion.
Zur Kenntnis neuer supraleitender Einlagerungsverbindungen von organischen Fünfring-Heterocyclen in 2H-Tantaldisulfid / New Superconducting Intercalation Compounds of Organic Five-Membered Heterocyclic Compounds with 2 Η-Tantalum Disulfide
Authors: Hummel Hans-Ulrich , Fackler Richard , Remmert Peter
Published: March 2015

The intercalation compounds TaS2(pyrrole)0.5 (1), TaS2(2-methylpyrrole)0.33 (2), TaS2(2,5-dimethylpyrrole) (3), TaS2(thiazole)0.33 (4) and TaS2(imidazole)0.33 (5) are formed readily in closed systems at temperatures up to 200°C. Furane and thiophene show no tendency to intercalate in 2H–TaS2. Compounds 2-5 are molecular intercalation species, and deintercalation is finished at 350°C, while in 1 the pyrrole guests have been associated and thermally induced deintercalation proceeds up to 900°C with fragmentation. 1-5 can be indexed on the basis of hexagonal symmetry assuming the space group P63/mmc. In 1 the stacking sequence of the host lattice TaS2 remains unchanged while in 2, 3 and 5 a transformation from the BaB CaC stacking of 2H –TaS2 to a sequence AbA AcA occurs. In 4 a stacking CbC BcB like in MoS2 is realized. 1-5 show superconducting behaviour at low temperatures, 2 exhibits a pronounced metall-semiconductor transition at 220 K.
Die Kristallstrukturen der Tetrafluoromanganate(III) AMnF4 (A = K, Rb, Cs) / The Crystal Structures of the Tetrafluoromanganates(III) AMnF4 (A = K, Rb, Cs)
Authors: Molinier Michel , Massa Werner
Published: March 2015

The crystal structures of AMnF4 compounds (A = K, Rb, Cs) were determined by X-ray diffraction on twinned single crystals: The K and Rb compound are isostructural: space group P21/a, Z = 4; KMnF4: lattice constants a = 769.9(2), b = 764.4(2), c = 576.9(1) pm, β = 90.54(3)°; R/wR = 0.029/0.025 for 481 reflections; pseudomerohedral (100) twin. RbMnF4: lattice constants a = 782.2(5), b = 777.7(3), c = 605.0(2) pm, β = 90.83(4)°; R/wR = 0.0665/0.0513 for 471 reflections. The structure of CsMnF4 has been refined anew in the space group P4/n (Z = 4) as a merohedral (110) twin (lattice constants a = 794.40(6), c = 633.76(9) pm; R/wR = 0.051/0.044 for 820 reflections). All three structures derive from the T1A1F4 type and show puckered [MnF4]- layers with an antiferrodistortive order of strongly Jahn-Teller distorted [MnF6] octahedra. The elongated axes (Mn-F for KMnF4: 215.8, RbMnF4 215.2, CsMnF4216.8 pm) alternate with shorter ones (188.1,188.3,185.4 pm) within the layer planes. The terminal Mn-F bonds are very short (180.3, 180.6,181.7 pm). The Mn-F-Mn bridging angles are 140.6° and 146.4° for the K, 148.3° and 152.1° for the Rb, and 161.9° for the Cs compound. The magnetostructural relations and the three puckering types are discussed for all the AMnF4 layered structures.
Kristallstruktur, thermische Zersetzung und Schwingungsspektrum von Ethylendiammonium-pentafluoromanganat(III), enH2MnF5 / Crystal Structure, Thermal Decomposition and Vibrational Spectrum of Ethylenediammonium-pentafluoromanganate(III), enH2MnF5
Authors: Bentrup Ursula , Schröder Ludger , Massa Werner
Published: March 2015

Single crystals of enH2MnF5 (en = ethylenediamine) have been prepared from aqueous HF solution and the crystal structure was determined by X-ray diffraction: space group Cccm, Z = 16, a = 1710.5(4), b = 1799.2(4), c = 847.8(2) pm, R/wR = 0.040/0.028 for 977 reflections. The structure consists of kinked [MnF5]2-- chains built by MnF6 octahedra sharing trans vertices (angles Mn-F-Mn 161.2 and 157.8°). The bridging Mn-Fax bonds are strongly elongated by the Jahn-Teller effect (mean Mn-Fax 215.4, Mn-F 183.8 pm). Each of the enH2
2+ cations is connected to four anionic chains by hydrogen bonds forming a 3 D network. Thermal decomposition occurs between 200 and 380 °C in two steps giving finally MnF2. The IR spectra of enH2MnF5 and its decomposition products are reported.
Silaheterocyclen, XVII / Silaheterocycles, XVII
Authors: Auner Norbert , Penzenstadler Erika
Published: March 2015

The silene 2 is formed by reacting 2-chloro-1,3-bis(trimethylsilyl)-2-vinyl-1,3-diaza-2-silacyclopentane (5) with LiBut in n-pentane in the temperature range from -10 to +10°C. The reaction primarily leads to the corresponding a-lithio adduct 6 by addition of the Li-organyl to the vinyl group of 5; subsequent 1,2-LiCl elimination yields 2 as an intermediate. 2 can be trapped by polar reagents Me3SiX (X = OMe, OSO2CF3) as well as by organic dienes which add across the Si=C bond; in the absence of trapping agents, trisilacyclohexane 7 is isolated. The cycloaddition behaviour of 2 is best described by the two mesomeric formulae (a) and (β), with competitive [4+2] and [2+2] addition routes: While with butadienes and norborna-2,5-diene the [2+2] products are formed mainly in a multiple step reaction via zwitterionic intermediates (1,4 dipoles), the ratio of the [4+2]/[2+2] derivatives from 2 and cyclohexa-1,3-diene becomes nearly equivalent. 2 is thus quite comparable in its reactivity to dichloroneopentylsilene, Cl2Si = CHCH2But.
Silaheterocyclen, XVIII Synthese und Cycloadditionsreaktionen C-silylmodifizierter aminocyclischer Silaethene [1] / Silaheterocycles, XVIII Synthesis and Cycloaddition Reactions of C-Silyl Modified Amino Cyclic Silenes [1]
Authors: Auner Norbert , Penzenstadler Erika
Published: March 2015

The reaction of 2-chloro-1,3-bis(trimethylsilyl)-2-(1′-trimethylsilyl-ethenyl)-1,3-diaza-2-silacyclopentane (5) and LiBu leads to the α-lithio adduct 8 which can be trapped by Me3Sitriflate to give 13b, and is a useful silene precursor. Subsequent 1,2-LiCl elimination yields 2 as an intermediate, which does not cyclodimerise giving a 1,3-disilacyclobutane, but can be trapped by Me3SiOMe and suitable dienes which add across the Si=C bond. In contrast to silene 1, which favours the [2+2] addition, 2 exclusively forms the Diels-Alder isomers with 2-methyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene (6 and 7), and the ene products 11 and 12 with norborna-2,5-diene and cyclohexa-1,3-diene, respectively. This quite different cycloaddition behaviour results from the substitution pattern at the Si=C framework, with a changing polarity. 2 thus appears to be a rather electron deficient silene having a polarity more comparable to that of diorganosilenes rather than to 1, which may be compared in its reactivity with Cl2Si = CHCH2Bu.
Tetraphenylphosphonium-nonachlorodivanadat(III), (PPh4)3[V2Cl9] · 7 CH2Cl2 / Tetraphenylphosphonium Nonachlorodivanadate(III), (PPh4)3[V2Cl9] · 7 CH2Cl2
Authors: Ruhlandt-Senge Karin , Bacher Alfred Dirk , Koellner Gertraude , Siewert Birgit , Müller Ulrich
Published: March 2015

Reaction of VC14 with (Me3Si)2S in CH2C12 yields an insoluble product with the approximate composition VSC12. Its reaction with PPh4Cl in CH2Cl2 affords (PPh4)3[V2Cl9] · 7 CH2Cl2, whereas PPh4[VOCl4] is formed in the presence of oxygen. According to an X-ray crystal structure analysis, (PPh4)3[V2Cl9] · 7 CH2Cl2 contains [V2C19]3- ions having two face-sharing coordination octahedra but no significant metal-metal bonding (V-V distance 327.5 pm). Crystal data: a = 1386.4(7), b = 1405.6(7), c = 2710(2) pm, α = 95.800(5), β = 95.370(5), γ = 118.11(3)°, triclinic, Ρ 1̄, Ζ = 2; R = 0.066 for 8779 observed reflexions. PPh4[VOCl4] is isotypic with AsPh4[VOCl4] and contains tetragonal-pyramidal [VOCl4]- ions; tetragonal, P4/n, Z = 2, a = 1264.5(2), c = 772.0(2) pm; R = 0.050 for 654 observed reflexions.
Conformational Analyses of Alkylated β-Cyclodextrins by NMR Spectroscopy
Authors: Meier-Augenstein Wolfram , Burger Barend V. , Spies Hendrik S. C. , Burger Wina J. G.
Published: March 2015

β-Cyclodextrin was derivatized with 1-bromoalkanes of different chain lengths. The yield as well as the purity of the resulting cyclodextrin derivatives were improved by using solvent mixtures instead of pure solvents. The heptakis(2,6-di-O-alkyl)- and heptakis(2,3,6-tri-O-alkyl)-β-cyclodextrins were studied by means of NMR spectroscopy employing one-dimensional as well as two-dimensional NMR techniques. Analysis of the NMR data showed that only in completely derivatized β-cyclodextrins the cyclodextrin torus undergoes a conformational change. Best separation factors were found for the cyclodextrin derivative with the highest internal mobility as determined from the corresponding NT1-values, the validity of which was confirmed by NOE determinations. Therefore, 13C relaxation times could be used as a measure of the efficiency and usefulness of a given cyclodextrin derivative as an enantioselective stationary phase.
Notizen: Ga0,5V2Se4, eine neue gemischtvalente Verbindung mit Spinellstruktur / Ga0,5V2Se4, a New Mixed Valence Compound with Spinel Structure
Authors: Haeuseler H. , Cordes W.
Published: March 2015

The mixed valence compound Ga0,5V2Se4 has been prepared and characterized by X-ray powder methods and infrared spectroscopy. The compound crystallizes in a spinel structure with 1:1 ordering on the tetrahedral sites. The lattice parameter of the cubic cell is a = 1013.8 pm.
Darstellung und Kristallstruktur der Verbindungen MnCuX (X = P, As, PxAs1-x) / Preparation and Crystal Structure of Compounds MnCuX (X = P, As, PxAs1-x)
Authors: Mündelein Joachim , Schuster Hans-Uwe
Published: March 2015

Three new ternary compounds MnCuP, MnCuP0.5As0.5 and MnCuAs have been prepared and characterized by X-Ray, DTA and magnetic measurements. They crystallize orthorhombically in the space group P nma (No. 62). The structures were calculated from single crystal data. The melting points were determined by DTA measurements (MnCuP: 1090°C; MnCuP0.5As0.5: 1000 °C; MnCuAs: 950 °C). MnCuAs appears to show an antiferromagnetic ordering up to 295 K.
High Mass Resolution Plasma Desorption and Secondary Ion Mass Spectrometry of Neutral Nickel Thiolate Complexes. Crystal Structure of [Ni6(SC3H7)12]
Authors: Feld Herbert , Leute Angelika , Rading Derk , Benninghoven Alfred , Henkel G. , Krüger Thomas , Krebs Bernt
Published: March 2015

The use of mass spectrometry for the analysis of transition metal complexes is demonstrated by combined high resolution Plasma Desorption Mass Spectrometry (PDMS) and Secondary Ion Mass Spectrometry (SIMS) investigations of the neutral nickel thiolate complexes [Ni4(SC3H7)8] (1), [Ni4(SC6H11)8] (2), [Ni8(SCH2COOEt)16] (3) and [Ni6(SC3H7)12] (4). The positive spectra are dominated by three kinds of SI-species: (a) molecular ions, (b) fragment ions and (c) molecular ions with one or more substrate atoms attached. The negative spectra show mainly nickel sulfur cluster ions of the composition (NixSy)-. In contrast to many Fast Atom Bombardment (FAB) spectra of neutral metal complexes, SIMS and PDMS spectra provide molecular weight as well as fragment ion information. Both techniques are most powerful tools for the investigation of coordination compounds because the samples are easy to prepare and the spectra are independent of matrix conditions. Additionally crystallographic studies have been carried out for 4. The hexanuclear complex 4 with square planar Ni-S coordination sites crystallizes in the trigonal space group R 3̅ with Z = 3 and α = 18.537(5), c = 13.966(3) Å.
Darstellung und Kristallstruktur von Na4Ga2S5. Ein Thiogallat mit -Zweier-Doppelketten / Preparation and Crystal Structure of Na4Ga2S5. A Thiogallate with --zweier-Double Chains
Authors: Klepp Kurt O.
Published: March 2015

Transparent single crystals of Na4Ga2S5 were obtained from a melt of Na2S, Ga and S. Na4Ga2S5 is monoclinic, space group P21/c with a = 7.967(1), b = 6.133(2), c = 19.852(9) Å, β = 91.61(2)°, Ζ = 4. Its crystal structure was refined to a conventional R of 0.033 for 1150 observed reflections.

The structure of Na4Ga2S5 is of a new type. It is characterized by infinite ribbon like thiogallate anions,

-, which are built up by GaS4-tetrahedra (mean Ga-S bond length 2.28 A) sharing apices and edges. The four crystallographically independent alkali cations are coordinated to six sulphur atoms in distorted octahedral configurations.