bluuebunny/crossref_metadata_2025 huggingface dataset:
Notizen: Synthese und Kristallstruktur von [OsCl4(CH3CN)2] · 1/2 CH3CN / Synthesis and Crystal Structure of [OsCl4(CH3CN)2] · 1/2CH3CN
Authors: Fenske Dieter , Baum Gerhard , Swidersky Hans-Walter , Dehnicke Kurt
Published: March 2015

[OsCl4(CH3CN)2] · 1/2CH3CN has been prepared by the reaction of OsCl5 with acetonitrile in a slow reaction at room temperature, forming red, moisture sensitive crystals. The compound was characterized by IR spectroscopy as well as by an X-ray structure determination. Space group Pnma, Z = 4, 1281 observed unique reflexions, R = 0.031. Lattice dimensions at 20 °C: a = 1032.5(5), b = 1356.0(7), c = 975.9(5) pm. The complex has a molecular structure, in which the osmium atom is octahedrally coordinated by four chlorine atoms and by two N-atoms of the ciscoordinated acetonitrile molecules. The included CH3CN molecules are disordered in two positions.
Notizen: Ethylenedioxytetrathiafulvalenes: New Unsymmetrical π-Donors
Authors: Papavassiliou G.C. , Lagouvardos D. J. , Kakoussis V. C. , Mousdis G. A.
Published: March 2015

Ethylenedioxybenzotetrathiafulvalene (EDOBTTF), ethylenedioxypyridino[4,5-b]tetrathiafulvalene (EDOP[4,5-b]TTF), ethylenedioxymethylenedithiotetrathiafulvalene (EDOMDTTTF), ethylenedioxyvinylenedithiotetrathiafulvalene (EDOVDTTTF), and ethylenedioxomethylenediselenotetrathiafulvalene (EDOMDSTTF) have been prepared and characterized analytically and spectroscopically.
Über das Hochdruckverhalten von Gips / On the Behaviour of Gypsum under High Pressure
Authors: Krüger Rolf-Rüdiger , Abriel Walter
Published: March 2015

The decomposition of gypsum (dehydration) was studied in the pressure range 7.5-60 kbar and the temperature range 75—400 °C using a belt type apparatus. Surprisingly, gypsum is rather stable even at pressures greater than 20 kbar contradicting the results of a calculation of the space requirement of the competing phases (AII—CaSO4 + H2O; Hemihydrate + H2O). Only when rising the temperature, as the most important thermodynamic variable for this reaction, the kinetically controlled decomposition starts. No accelleration of the dehydration process under shear stress (simple squeezer device) could be detected due to the limited (not geological) time.
Azaborolyl-Komplexe, 25 Das (1-tert-Butyl-2-methyl-1 H-1,2-azaborolyl)cobalt-Fragment (AbCo) als Synthesebaustein / Azaborolyl Complexes, 25. The (1-tert-Butyl-2-methyl-1 H-1,2-azaborolyl)cobalt Fragment (AbCo) as Building Block in Synthesis
Authors: Schmid Günter , Boutrid Abdel K. , Kreuzer Eva-Maria
Published: March 2015

The (1-tert-butyl-2-methyl-1 H-1,2-azaborolyl)cobalt fragment (AbCo), available from AbCo(C2H4)2 (1), serves as a building block in a series of complexes and clusters. The mononuclear complexes AbCo(C2H4)PMe3 (2), AbCo(PMe3)2 (3), AbCo(C2H4)P(OMe)3 (4), AbCo(P(OMe)3)2 (5), AbCo(C2H4)CO (6), and AbCo(CO)2 (7) are easily prepared from 1. AbCo(CpH) (8) is formed from 1 and CpCo(C2H4)2 together with AbCp3Co4H4 (9). The tetranuclear cluster Ab4Co4H4 (10) results, if 1 is warmed to 80 °C without a solvent. Ab3(CO)3Co3 (11) is available by a co-thermolysis of 1 and 7. Thermolysis of 6 leads to the trinuclear cluster Ab3(CO)2Co3 (12). Photolytical degradation of 7 forms the dinuclear complex Ab2(CO)3Co2 (13). Mass spectrometry, IR spectroscopy, and NMR investigations serve to elucidate the molecular structures.
Bildung und Kristallstruktur von Ethylendiammonium-hydridotrioxophosphat(2–) [H3NCH2CH2NH3][PHO3]a / Formation and Crystal Structure of Ethylenediammonium Hydridotrioxophosphate(2—) [H3NCH2CH2NH3][PHO3]
Authors: Hönle Wolfgang , Walz Leonhard , Schnering Hans Georg von
Published: March 2015

Ethylenediammonium Hydridotrioxophosphate(2–) [H3NCH2CH2NH3][PHO3] is formed by slow oxidation of white phosphorus by oxygen in ethylendiamine. It crystallizes in the space group Pbca with a = 1570.6(4) pm, b = 676.9(5) pm, c = 1267.8(4) pm and Z = 8 formula units in the unit cell. The structure is built from ethylenediammonium dications and tetrahedral phosphonate dianions, linked by O ··· H–N bonds (d̄(O…N) = 275.8 pm). The bond distances are d̄(P–O) = 151.8 pm, d̄(P–H) = 136.9 pm, d̄(N–C) = 148.3 pm and d̄(C–C) = 151.0 pm.
Beiträge zur Chemie des Phosphors, 208 [1] / Contributions to the Chemistry of Phosphorus, 208 [1]
Authors: Baudler Marianne , Hahn Josef
Published: March 2015

The valence tautomerism of the heptaphosphanortricyclene anion P7
3- has been studied by means of a two-dimensional 31P NMR exchange spectrum. The rearrangement process of the P atoms postulated earlier [2] has been confirmed in all details.
Notizen: Molekülstruktur von (Z) – N –[4-(Dimethylamino)phenyl]-α[2-(methoxy)phenyl]ethanimin / Molecular Structure of (Z) — N — [4-(Dimethylamino)phenyl]-α[2-(methoxy)phenyl]ethaneimine
Authors: Thewalt Ulf , Bachus Herbert , Brune Hans-Albert
Published: March 2015

The molecular structure of the title compound was determined in order to obtain structural information for an imine that can be catalytically hydrogenated with rhodium(I) complexes. The imine part of the molecule is almost planar. The two phenyl rings form angles of 66.3 and 52.0°, respectively, with the imine plane.
Kupfer(I)-Komplexe mit ungesättigten Stickstoffliganden, V / Kupfer(I)-Komplexe mit Diazadienen als Chelate und Brücken: Röntgenstrukturenuntersuchungen an (DAD)Cu(μ-Cl)2Cu(DAD), [(DAD)2Cu]⁺ (CuCl2)-, (DAD)CuCl, [μ-(DAD)2Cu5Cl5]n und [μ-(DAD)Cu(OTf)]n (DAD = Diazadien) / Copper(I) Complexes with Unsaturated Nitrogen Ligands, V Copper(I) Complexes with Chelating and Bridging Diazadienes: X-Ray Diffraction Studies of (DAD)Cu(μ-Cl)2Cu(DAD), [(DAD)2Cu]+ (CuCl2)-, (DAD)CuCl, [μ-(DAD)2Cu5Cl5]n and [μ-(DAD)Cu(OTf)]n (DAD = Diazadiene)
Authors: Dieck Heindirk tom , Stamp Lutz
Published: March 2015

Diazadienes RN = CR′-CR′ = NR (DAD) form molecular complexes with copper(I) halides of composition (DAD)CuX, the structures of which vary from [(DAD)2Cu]+(CuCl2)⁻ with a non-tetrahedral bis(chelated) cation, over [(DAD)CuCl]2 with asymmetrically bridging chloro ligands to planar three-coordinate (DAD)CuCl. The composition of the isolated complexes depends on the relative concentrations or on the solvent. The “soft” coordination geometry of copper is underlined by the structure of the coordination polymer of composition (DAD)2Cu5Cl5, in which Cu atoms of coordination number 2, 3 and 4 and very irregular geometries are encountered and where the DAD ligands are exclusively bridging. Halide ions and sp2-nitrogen donors are very competitive. Bridging DAD ligands are also encountered in (DAD)Cu-Y with the less nucleophilic anions trifluoromethane-sulphonate or perchlorate. Crystal and molecular structures are established for all these coordination geometries and the causes are discussed for the coordination flexibility of copper(I)
Synthese und Kristallstruktur von [VCl2(15-Krone-5)]+[VOCl4]- / Synthesis and Crystal Structure of [VCl2(15-Crown-5)]+[VOCl4]-
Authors: Frenzen Gerlinde , Massa Werner , Ernst Thilo , Dehnicke Kurt
Published: March 2015

[VCl2(15-crown-5)]+[VOCl4]- has been prepared by the reaction of VCl4 with 15-crown-5 in acetonitrile solution in the presence of water, forming black-brown single crystals. They were characterized by IR spectroscopy as well as by an X-ray structure determination. Space group Pnma, Z = 4, 1530 observed unique reflexions, R = 0.052. Lattice dimensions at -120°C: a = 1128.5(4), b = 1063.3(3), c = 1680(1) pm. The compound forms ions, in which the cation contains vanadium(+III), which is seven coordinate by the five oxygen atoms of the crown ether molecule and by two chlorine atoms in axial positions of a pentagonal bipyramide. The [VOCl4]- anion contains vanadium (+V) with approximately tetragonal symmetry
Verbindungen mit dem 1,3-Dimethyl-1,3-diaza-2-phosphetidin-4-on-Grundgerüst; Synthese von 1,3-Dimethyl-2-thia-1,3-diaza-2 λ4-phosphetidin-4-on-Derivaten / Compounds Involving the 1,3-Dimethyl-1,3-diaza-2-phosphetidine-4-one Structure; Synthesis of 1,3-Dimethyl-2-thia-1,3-diaza-2λ4-phosphetidine-4-one Derivatives
Authors: Breker Johannes , Wermuth Ulrich , Schmutzler Reinhard
Published: March 2015

In the reaction with hexamethyldisilthiane the cyclic trichlorophosphorane O=C(NMe)2PCl3 (1) was converted to the new compound O=C(NMe)2P(=S)Cl (2). A range of derivatives, O=C(NMe)2P(=S)Y (Y=NR2, OMe, SMe, 3-7) was obtained in the reaction of 2 with the appropriate trimethylsilyl derivatives, Me3SiY. The compounds 8 and 9 (Y=NPh2 and N(C6H11)2) could not be synthesized by this route as the required trimethylsilyl derivative was not reactive enough (Me3SiNPh2) or was not available (Me3SiN(C6H11)2), presumably on account of the bulk of the NPh2 and N(C6H11)2 groups. 8 and 9 could be prepared by an alternative route, i. e. by addition of elemental sulphur to the λ3P-diazaphosphetidinones, O=C(NMe)2PNR2 (R=Ph, C6H11), 10 and 11. Identity and structure of the new compounds were established on the basis of their elemental analyses and 1H, 13C and 31P NMR studies
Radiolysis of Tertiary Butyl Hydroperoxide in Aqueous Solution. Reductive Cleavage by the Solvated Electron, the Hydrogen Atom, and, in Particular, the Superoxide Radical Anion
Authors: Phulkar Shailesh , Rao Balijepalli Sethu Madhava , Schuchmann Heinz-Peter , Sonntag Clemens von
Published: March 2015

The reactions of the solvated electron, the H atom, the OH radical and the superoxide radical anion with t-butylhydroperoxide (t-BuOOH) have been studied in aqueous solutions using γ-radiolysis and pulse radiolysis to generate these radicals.

The solvated electron reacts rapidly with t-BuOOH (k=5 × 109dm3mol-1 s-1) yielding t-BuO· and ·OH in a ratio of 4:1. The yield of t-BuO· has been determined by measuring its fragmentation product, acetone.

The H atom reacts more slowly with t-BuOOH (k=5 × 10 7 dm3 mol-1 s-1). There is very little H-abstraction from the methyl and the hydroperoxyl groups (about 3%), the main reaction again being the scission of the hydroperoxyl function with a branching ratio t-BuO·/·OH of about unity.

The OH radical reacts with t-BuOOH considerably more slowly (k=8 × 10 7 dm3 mol-1 s-1) than with t-butanol (k=5 × 108 dm3 mol-1 s-1) with an approximate preference of 8:1 of abstracting a methyl hydrogen over a hydroperoxyl hydrogen atom. The carbon-centered radical undergoes γ-cleavage (k ≈ 102 s-1) thereby reforming an OH radical. The resulting chain reaction is rather short (maximum yield G(2-methyl-1,2-epoxypropane), 26 × 10-7 mol J-1 at low dose rate) due to H-abstraction at the hydroperoxyl function of t-BuOOH by the OH radical.

The superoxide radical anion also reacts with t-BuOOH by cleaving the hydroperoxyl function. Its reactivity is, however, rather low (k=5 dm3 mol-1 s-1)
Notizen: Darstellung und Struktur von LiPd2Tl / Preparation and Structure of LiPd2Tl
Authors: Schuster Hans-Uwe , Czybulka Axel , Last Detlef
Published: March 2015

A new ternary phase LiPd2Tl has been synthesized. It crystallizes in a modified tetragonal Al3Ti-type-structure with the lattice constants a = 413.7(1) pm, b = 731.8(2) pm
Metal Tetrahydroborates and Tetrahydroborato Metalates, 16 [1]. An 11B and 113Cd NMR Investigation of the CdI2—MBH4 System in Dimethylformamide and Diglyme [2]
Authors: Nöth Heinrich , Thomann Martina
Published: March 2015

CdI2 dissociates in dimethylformamide (DMF) into Cd(DMF)6
2+, CdI(DMF)5
+, CdI3- and CdI4
2-. Rapid scrambling occurs at ambient temperature in DMF solutions containing CdI2 and MBH4 (M = Na, Li). At 213 K these exchange processes are slowed down to allow the detection of CdI4
2-, CdI3
-, CdI3(BH4)2-, CdI2(BH4)2
2-, CdI(BH4)3
2-, CdI(BH4)2- and Cd(BH4)3
- by 113Cd NMR spectroscopy. The BH4 groups are bound to the Cd centre via two hydrogen atoms as derived from the multiplicity of the 113Cd signals. CdI2 dissolves in diglyme as a molecular entity. Its reaction with M BH4 proceeds via solvated CdI(BH4) and Cd(BH4)2 to CdI(BH4)3
2- and Cd(BH4)3
-. Solubility restriction prevent a 113Cd NMR study of solutions in which the MBH4 : CdI2 ratio exceeds 1:1.
Metal Tetrahydroborates and Tetrahydroborato Metalates, 17 / Bonding in Cadmium Bis(tetrahydroborate), and the Reaction with Lithium Tetrahydroborate
Authors: Nöth Heinrich , Thomann Martina
Published: March 2015

Cadmium bis(tetrahydroborate) has been prepared from dimethyl cadmium and H3B · THF in tetrahydrofuran. Low temperature 113Cd NMR spectra recorded for THF, monoglyme and diglyme solutions show a septet with 1J(113Cd1H) = 273 Hz. This proves that the BH4⁻ groups are bound to the metal centre via triple hydride bridges. Reaction of Cd(BH4)2 with LiBH4 yields LiCd(BH4)3 quantitatively in diglyme solution.
Zur Kenntnis von Be[C2(COO)2] · 4 H2O — Ein durch starke Wasserstoffbrückenbindungen stabilisiertes anorganisches Derivat der Acetylendicarbonsäure / On Be[C2(COO)2] · 4 H2O — An Inorganic Derivative of Acetylenedicarboxylic Acid Stabilized by Strong Hydrogen Bonding
Authors: Robl Christian , Hentschel Stephanie
Published: March 2015

Colorless orthorhombic single crystals of Be[C2(COO)2] · 4 H2O were grown in aqueous silica gel. Space group Cmcm, α = 1004.7(1), b = 675.0(1), c = 1262.4(2) pm, Rg = 0.0264. The crystal structure consists of Be(H2O)4
2+ tetrahedra and planar [C2(COO)2]2- anions linked together by strong asymmetric hydrogen bonds. A layer-like arrangement extending parallel (010) made up by [C2(COO)2]2- anions and hydrogen bound water molecules of the Be(H2O)4
2+ tetrahedra is the primary structural feature of Be[C2(COO)2] · 4H2O. These layers are stacked and interlinked by coordinative bonds between Be2+ and H2O to yield a rigid three-dimensional framework. Thermal decomposition commences with endothermic loss of water of crystallisation at 160 °C followed by several steps of exothermic degradation yielding finally a soot-like amorphous residue.
Synthese und Struktur von Thiolatokomplexen des einwertigen Kupfers: Tetrameres und Octameres [CuSC6H2(i-Pr)3] / Synthesis and Structure of Thiolato Complexes of Monovalent Copper: Tetrameric and Octameric [CuSC6H2(i-Pr)3]
Authors: Schröter-Schmid Ingrid , Strähle Joachim
Published: March 2015

[CuSC6H2(i-Pr)3]n = 4 (1), and n = 8 (2) are obtained from CuCO3 · Cu(OH)2 and 2,4,6-tri(isopropyl)thiophenol in a slow reaction, where long reaction times promote the formation of octameric 2.1 crystallizes as colorless platelets, space group C 2/c: a = 3647(2), b = 854.8(6), c = 2061.3(7) pm, β = 105.98(4)°, Ζ = 4. Central unit of the tetrameric complex with the symmetry C2 is a non planar eight-membered Cu–S heterocycle. The four Cu atoms form a rhombus with short edges of 269.7 and 270.1 pm. The bridging SR-ligands are arranged alternatingly above and below the Cu4 rhombus. Octameric 2 crystallies as 2•(H2O)x in the form of orthorhombic yellow blocks, space group Pbcn: a = 2513(1), b = 1975(1), c = 2747(1) pm, Z = 4. The thiolato ligands connect the Cu atoms to form a folded 16-membered Cu–S ring with the symmetry C2. The eight S atoms are arranged at the corners of a cube with the Cu atoms occupying eight of its edges. The Cu–Cu distances are in the range of 267.8 to 304.0 pm. In 1 as well as in 2 the Cu atoms are linearly coordinated with Cu–S distances of 214.7 to 217.9 pm.
Position 10 is Critical for Antagonists of the Luteinizing Hormone-Releasing Hormone and for Inhibition of Ovulation in Rats
Authors: Feng Dong-Mei , Ljungqvist Anders , Hook William A. , Bowers Cyril Y. , Folkers Karl
Published: March 2015

Eleven analogs of the luteinizing hormone-releasing hormone (LHRH) have been designed, synthesized, bioassayed and compared for antiovulatory activity (AOA) in rats. The emphasis of design was on analogs with D–Ala10, Sar10, D–Ser10, (desGly10, NHEt), D–Abu10, Gly10, and with substitutions in position 5, 6, and 8.

High antiovulatory activity was obtained with analogs having D– Ala in position 10. Four earlier analogs, 1, 4, 11 and 13, with D– Ala in position 10, showed 67-100% AOA at 0.25 μg in rats. Analog 1 showed 60% AOA at 0.125 μg. The replacement of D–Ala10 in analog 11 by Sar10 in analog 12, retained activity, 62% vs. 67% AOA at 0.25μg, 100% vs. 90% AOA at 0.5 μg. This analog with Sar10 was the only one that did not show substantial loss of activity upon replacement of D–Ala10.
A Convenient Solid-Support Procedure for the Synthesis of Symmetric Disulphides. The Configuration of Aromatic Carben Atoms in the 1,6-Methano[10]annulene Framework
Authors: Neidlein Richard , Constantinescu Take , Krieger Claus , Deigner H.-P.
Published: March 2015

Treatment of organic thiocyanates with aluminium oxide, at room temperature, is found to afford a convenient procedure for the synthesis of symmetric disulphides, under mild conditions.

An X-ray structure analysis of meso-di-(1,6-methano[10]annulen-2-yl)-disulphide (2a) suggests an intermediate sp2—-sp3 hybridization state for the aromatic carbon atoms and a faceasymmetric electronic distribution in the annulene ring. Using reported atomic coordinates, a similar configuration is determined for the parent structure 7. A higher π-electron density on the exo face of the aromatic ring may account for the known syn,syn stereochemical course of electrophilic addition to 7, as well as for the high reactivity of this system towards electrophiles, in addition and in substitution reactions.
Cu2Zn2Superoxide Dismutase Activity in an Air Dried Egyptian Mummy of the New Kingdom
Authors: Weser Ulrich , Miesel Ralf , Heizmann Wolfgang , Hartmann Hans-Jürgen
Published: March 2015

The structural intactness of many biopolymers in mummified tissues is well documented. By way of contrast no functional evidence of an isolated protein is known. The well defined air dried mummy of a deceased 16±2 year male teenager 1200 B. C. prompted us to search for the possible presence and function of Cu2Zn2superoxide dismutase or remnants thereof. Using two different assay systems unequivocal proof of a specific Cu2Zn,superoxide dismutase activity in brain extract was demonstrated. Fast protein liquid chromatography of the extract on Superose 12 revealed an approx. 5 kD Cu-containing polypeptide to which activity was assigned. It is assumed that during the ageing process considerable portions of the 31.3 kD homodimer were cleaved leaving this active core up to the present date. This would be the first case of the presence of an enzymically active component surviving the past 3000 years of mummification.
Notizen: Kristallstruktur von [Cu4OCl6(CH3CN)4] · 2 CH3CN / Crystal Structure of [Cu4OCl6(CH3CN)4] · 2 CH3CN
Authors: Hiller Wolfgang , Zinn Alfred , Dehnicke Kurt
Published: March 2015

The title compound has been prepared by the reaction of CuCl, with hexakis(trimethylsilyl)-benzdiamidine, in boiling acetonitrile in the presence of traces of water, as brown crystals, which were characterized by their IR spectrum as well as by an X-ray structure determination. Space group C 2/c, Z = 4, 2668 observed unique reflexions, R = 0.036. Lattice dimensions at –65 C: a = 879.5(2), b = 2441.1(3), c = 1241.4(3) pm, β = 95.24(3)°. In the structure four copper atoms surround an oxygen atom in a slightly distorted tetrahedral fashion; the chlorine atoms bridge adjacent copper atoms, and each copper atom is thus bound to three chlorine atoms. The nitrogen atoms of the acetonitrile complete the slightly distorted trigonal bipyramid around the copper atoms.
Neue A4B3-Moleküle: P3SbS3, P4S2Te und P4STe2 / New A4B3 Molecules: P3SbS3, P4S2Te and P4STe2
Authors: Baldus Hans Peter , Blachnik Roger
Published: March 2015

The new molecules P3SbS3, P4S2Te und P4STe2 were extracted with CS2 from mixtures of S. Sb and P4S3, and P, S and Te samples respectively, which were previously molten and then annealed for several days. In the P3SbS3 molecules the apical phosphorus position of P4S3 is substituted by antimony. In the molecules P4STe2 and P4S2Te one or two of the sulphur bridges are substituted by tellurium. X-ray and 31P NMR data of the compounds are given.
Halogen-Pseudohalogen-Austausch an Bromsulfoniumsalzen. Dimethylthiocyansulfonium- und Dimethylselenocyansulfonium-Hexafluoroarsenat/ Halide-Pseudohalide Exchange with Bromosulfonium Salts. Dimethylthiocyanosulfonium- and Dimethylselenocyanosulfonium-Hexafluoroarsenate
Authors: Minkwitz Rolf , Gerhard Volker , Preut Hans
Published: March 2015

The preparation and spectroscopic characterization of the sulfonium salts (CH3)2SSCN+AsF6-, (CH3)2SSeCN+AsF6- and (CH3)2SNCO+AsF6
- is reported. The compounds are obtained via halide-pseudohalide exchange reactions with (CH3)2SBr+AsF6
- and the corresponding silver pseudohalide. In addition the crystal structure of (CH3)2SSCN+AsF6
- was determined. The salt crystallizes in the orthorhombic space group Pbca with a = 1048.4(9) pm, b = 1290.2(6) pm, c = 1405.1(12) pm and Z = 8.
Electrochemical Syntheses of Pyrimidine-2-thiolato Complexes of Nickel(II) / Crystal and Molecular Structure of 2,2′-Bipyridine-bis(pyrimidine-2-thiolato)nickel(II) Monohydrate
Authors: Castro R. , Durán M. L. , García-Vázquez J. A. , Romero J. , Sousa A. , Castiñeiras A. , Hiller W. , Strähle J.
Published: March 2015

The electrochemical oxidation of nickel in pyrimidine-2-thione (pymt H) solution yields a compound of formula [Ni(pymt)2]. When pyridine (py), 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) are added to the solution phase, the product obtained is a complex [Ni(pymt)2py2] or [Ni(pymt)2L] (L = bipy or phen). The crystal structure of [Ni(pymt)2bipy] · H2O is monoclinic, space group P 21/c, with a = 726.6(2), b = 1586.2(2), c = 1696.7(4) pm, β = 99.04(4)° and Z = 4. The nickel atom has highly distorted octahedral coordination and the pyrimidine-2-thiolato ligand is bidentate, forming two four-membered chelate rings with a small “bite” angle of ca. 68°. The two sulphur atoms are in a trans arrangement. The vibrational and electronic spectra of the compounds are discussed.
Über die Darstellung der (Chlorthio)sulfoniumsalze [(CH3)2SSSCl]+SbF6
-, [(CH3)2SSCl]+SbF6
- und des isomeren [(CH3)(Cl)S – SCH3]+SbCl6
- / On the Preparation of the (Chlorothio)sulfonium Salts [(CH3)2SSSCl]+SbF6-, [(CH3)2SSCl]+SbF6
- and the Isomer [(CH3)(Cl)S–SCH3]+SbCl6
-
Authors: Minkwitz Rolf , Kornath Andreas , Krause Renate , Preut Hans
Published: March 2015

The preparation of the stable compounds [(CH3)2SSCl]+SbF6
- and [(CH3)2,SSSCl]+SbF6
- from [(CH3)2SH]+SbF6- and SCl2 and S2Cl2, resp., is reported.

The isomer [(CH3)(Cl)S–SCH3]+SbCl6
- is prepared from [SCl3]+SbCl6
- and CH3SH in the molar ratio 1:2. For this salt a crystal structure analysis was carried out (Space group P212121, Z = 4, a = 750.1(4), b = 1133.7(3), c = 1614.8(3) pm).
Darstellung und Kristallstruktur von Cs2Sn3Se7, ein Cäsium-selenostannat(IV) mit fünffach koordiniertem Zinn / Preparation and Crystal Structure of Cs2Sn3Se7, a Cesium Selenostannate(IV) with Pentacoordinated Tin
Authors: Sheldrick W. S. , Braunbeck H.-G.
Published: March 2015

Methanolothermal reaction of Cs2CO3 with SnSe, in the presence of SnSe at 160 C and 13 bar yields the selenostannates(IV) Cs4Sn2Se6 and Cs,Sn3Se7. The structure of the latter phase was established by X-ray structural analysis. The crystal structure contains polyselenostannate(IV) sheet anions [Sn3Se7
2-]∞2, for which the basic elements are trigonal SnSe5-bipyramids. Six of the seven independent selenium atoms in the asymmetric unit are coordinated by two tin atoms, one by three atoms. Neighbouring anion sheets are so placed that channels are formed which contain two independent cesium cations; these display coordination numbers of, respectively, eight and seven.
Chiral Lewis Acids as Enantioselective Catalysts in the Diels-Alder Reaction and the Allylic Addition to Aldehydes
Authors: Ketter Andreas , Herrmann Rudolf
Published: March 2015

The efficiency of chiral Lewis acids derived from TiCl4 or Al(Bui)2Cl with chiral chelating ligands as catalysts for some enantioselective reactions was evaluated. The Diels-Alder reaction between isoprene and methyl acrylate gave the cyclohexene derivative with up to 32% enantiomeric excess (e. e.). The reaction of 3-methylbutanal with allyltrimethylsilane led to 6-methylhept-1-en-4-ol with up to 36% e. e.
Synthese der vorgeschlagenen Sequenz für ein neues Thymosin aus Forellenmilz / Synthesis of a New Thymosine from Trout Spleen
Authors: Voelter Wolfgang , Kalbacher Hubert , Echner Hartmut , Schmid Bettina , Treffer Udo , Schröder Christoph
Published: March 2015

Thymosine β11, a peptide structurally very similar to the known thymosine β11, was recently isolated from trout spleen and synthesized by the solid phase method using the p-benzyloxybenzyl alcohol/polystyrene/divinylbenzene resin, Nα-Fmoc-amino acids and those with tert-butyl or Boc side chain protection. All couplings are performed with the DCC reagent. The peptide is purified by a combination of gel chromatography and preparative HPLC.
Triorganoblei- und Triorganozinnderivate von Hydroxyaminosäuren und O-Acetylserin / Triorganolead and Triorganotin Derivatives of Hydroxyamino Acids and of O-Acetylserine
Authors: Mundus-Glowacki Brigitte , Huber Friedo
Published: March 2015

Bis(triphenyllead) compounds (Ph3Pb)2A [H2A = H2Ser (= L-serine), H2Tyr (= L-tyrosine), H2Phoser (= phosphorylserine)], R3PbAcSer (HAcSer = O-acetylserine; R = Ph, Me) and Ph3SnAcSer have been prepared from R3MOH and the appropriate amino acids. From IR data it is inferred that all compounds are polymeric, and that (Ph3Pb)2A (A = Ser, Tyr) and Me3PbAcSer contain unsymmetrically bridging carboxylate groups and coordinating NH2. For (Ph3Pb)2Phoser a structure with a monodentate carboxylate group and intermolecular coordination of Pb by an NH2- and a P=O-group is proposed. The molecules of Ph3MAcSer (M = Pb, Sn) containing monodentate carboxylate groups are bridged by acetyl-C=O groups.
TaI2Cl2, eine neue Verbindung vom MX4-Typ (M=Nb, Ta; X=Cl, Br, I) / TaI2Cl2, A New Compound of the MX4-Type (M=Nb, Ta; X=Cl, Br, I)
Authors: Meyer H.-Jürgen
Published: March 2015

The new compound TaI2Cl2 is formed from the reaction of TaCl5 with Tal5 and Ta powder in sealed Ta containers at 450 °C. The crystal structure contains quasi one-dimensional chains of TaI4/2Cl2 octahedra, sharing opposite edges (orthorhombic, Immm, a = 831.5(5) pm, b = 993.7(4) pm, c = 748.5(4) pm; R = 0.037 for 297 independent intensities). Each chain has two Ta bridging iodine bonds alternating in length along the chain direction yielding short (314.9(2) pm) and long (433.6(3) pm) Ta-Ta distances. The electronic structure indicates a Peierls-type stabilization.
Über die Reaktion von C(NMe2)4 mit zweikernigen Übergangsmetallcarbonylen; Kristallstrukturen von [C(NMe2)3][Mn(CO)5] und [C(NMe2)3][Co(CO)4] / On the Reaction of C(NMe2)4 with Binuclear Transition Metal Carbonyls: Crystal Structures of [C(NMe2)3][Mn(CO)5] and [C(NMe2)3][Co(CO)4]
Authors: Petz Wolfgang , Weller Frank
Published: March 2015

The reactions of C(NMe2)4 (1) with Mn2(CO)10 or Co2(CO)8 in THF yield

[C(NMe2)3][Co(CO)4] (3) and [C(NMe2)3][Mn(CO)5] (4), respectively. The compounds Co(CO)4NMe2 (5) and Mn(CO)5NMe2 (6) could not be found. With CH2Cl2 4 is quantitatively converted into [C(NMe2)3][Mn(CO)4Cl2] (7) as shown by IR and 13C NMR investigations. 3 and 4 were characterized by an X-ray structure determination. 3: Space group Pnma, Z = 4, a = 7.435(2), b = 10.79(2), c = 20.299(5)Å. 4: Space group C2/c, Z = 4, a = 11.378(2), b = 10.165(1), c = 14.533(1) Å; β = 103.37(1)°. The compounds form independent ions with no bonding interactions between cation and anion; the central CN3 unit of the [C(NMe2)3]+ cation in 3 and 4 is disordered.
Übergangsmetallkomplexe mit Schwefelliganden, LVIII / Transition Metal Complexes with Sulfur Ligands, LVIII
Authors: Sellmann Dieter , Neuner Hans-Peter , Moll Matthias , Knoch Falk
Published: March 2015

The monocation [Ru(′S6′–CH=CH2)]+, [2]+, (′S6′–CH=CH2
- = 2.3.11.12-dibenzo-1.4.7.10.13.16-hexathiaoctadec-17-ene(1–)) forms under normal conditions by S–C bond cleavage in an irreversible and selective reaction on treating salts of the dication [Ru(bzo2-18S6)]2+, [1]2+, (bzo2-18S6 = 2.3.11.12-dibenzo-1.4.7.10.13.16-hexathiacyclooctadecane) with one equivalent of base. This reaction demonstrates the drastic S–C activation in coordinated thioethers and should be taken into consideration when cofactors are isolated from metal sulfur enzymes.
Notizen: Distinguishing Kinetically between Reaction Types A + B → C and A + 2 B → C + B. The Relevance to the Alcoholysis of Ketenes and Related Reactions
Authors: Satchell Derek P. N. , Satchell Marcel J. F.
Published: March 2015

An apparent discrepancy between the kinetics reported for the alcoholysis of ketenes is resolved by examining conditions under which third-order kinetic behaviour can be mistaken for secondorder behaviour.
Notizen: Die Kristallstruktur von [(CH3)4N]FeF4 · H2O mit einem di(µ-fluoro)-verbrückten [Fe2F8(H2O)2]2–-Anion / Crystal Structure of [(CH3)4N]FeF4 · H2O with a Di(μ-fluoro)-Bridged [Fe2F8(H2O)2]2- Anion
Authors: Bentrup Ursula , Massa Werner
Published: March 2015

Single crystals of [(CH3)4N]FeF4·H2O have been prepared from aqueous HF solution. The crystal structure was determined by X-ray diffraction: space group P1̄, Z = 2 (or 1 dimeric unit), a = 705.7(5), b = 818.5(8), c = 915.2(12) pm, α = 65.46(10)°, β = 82.90(9)°, γ = 72.76(7)°, R/wR = 0.047/0.021. The structure consists of centrosymmetrical dimeric anions [Fe2F8(H2O)2]2- with fluorine double bridges and is isotypic with [(CH3)4N]VOF3 · H2O. Intramolecular H-bonds are found between the axial water and fluoride ligands. By additional strong intermolecular H-bonds (O ··· F 258 pm) the anions are connected to form infinite parallel chains between which the TMA cations are located. [(CH3)4N]AlF4 · H2O is shown to be isotypic.
Niob-Stickstoff-Verbindungen: Synthese und Struktur der Halbsandwichkomplexe Ph3P = N–Nb(η5-C5EtMe4)Cl3 und [(η5-C5EtMe4)Cl3Nb–N = PPh2]2C2H2 / Niobium Nitrogen Complexes: Synthesis and Structure of Halfsandwich Complexes Ph3P=N–Nb(η5-C5EtMe4)Cl3 and [(η5-C5EtMe4)Cl3Nb–N = PPh2]2C2H2
Authors: Leichtweis Iring , Roesky Herbert W. , Noltemeyer Mathias , Schmidt Hans-Georg
Published: March 2015

Cp*NbCl4 (1) (Cp* = η5-C5Me5) and (η5-C5EtMe4)NbCl4 (2) are synthesized in moderate yields by reaction of NbCl5 with the corresponding silanes.

Compound 1 reacts with Me2S(O)=NSiMe3 (3) or Ph3P=NSiMe3 (4) to form the complexes Me2S(O)=N–NbCp*Cl3 (5) and Ph3P=N–NbCp*Cl3 (6). Treatment of 2 with 4 or (Me3SiN=PPh2)2C2H2 (7) yields Ph3P=N–Nb(η5-C5EtMe4)Cl3 (8) and [(η5-C5EtMe4)Cl3Nb-N=PPh2]2C2H2 (9). Products 8 and 9 were characterized by X-ray structure analysis.
Synthesis of Some Pyrazolopyridine Sulphonamide Derivatives
Authors: El-Dean A. M. Kamal , Atalla A. A. , Mohamed Th. A. , Geies A. A.
Published: March 2015

The diazonium salt of 3-aminopyrazolopyridine when treated with SO2 and CuCl2 produces the corresponding sulphonyl chloride. The sulphonyl chloride chloride easily reacts with hydrazine hydrate, ammonia, aromatic or heterocyclic amines to produce the corresponding sulphohydrazide, sulphonamide or N-sulphonamide derivatives. Sulphohydrazide reacts with acetylacetone to produce pyrazoly pyrazolopyridinyl sulphone which is also obtained by reaction of sulphonyl chloride with dimethylpyrazole. The aminopyrazolopyridine can be converte into pyrazolopyridinthiole by its reacting with ethyl dithioxanthate. The pyrazolopyridinthiole reacts with alkyl halides or acrylonitrile to produce S-alkylated derivatives.
Die Kristallstrukturen der isotypen Verbindungen Ba3[MoN4] und Ba3[WN4] / The Crystal Structures of the Isotypic Compounds Ba3[MoN4] and Ba3[WN4]
Authors: Gudat Axel , Höhn Peter , Kniep Rüdiger , Rabenau Albrecht
Published: March 2015

The isotypic ternary compounds Ba3[MoN4] and Ba3[WN4] were prepared by reaction of the transition metals with barium (Ba3N2, resp.) under nitrogen. The crystal structures were determined by single crystal X-ray diffraction: Ba3[MoN4] (Ba3[WN4]): Pbca; Z = 8; a = 1083.9(3) pm (1091.8(3) pm), b = 1030.3(3) pm (1037.5(3) pm), c = 1202.9(3) pm (1209.2(4) pm). The structures contain isolated tetrahedral anions [MN4]6- (M = Mo, W) which are arranged in form of slightly distorted hexagonal layers and which are stacked along [010] with the sequence (···AB···). Two of the three Ba atoms are situated between, the third one is placed within the layers of [MN4]-groups. In this way the structures can be derived from the Na3As structure type.
Einfluß des Kations auf die Struktur des [Si(O2C6H4)2F]⊖-Anions: Struktur von [K(18-Krone-6)][Si(O2C6H4)2F] / The Influence of the Cation on the Structure of the Anion [Si(O2C6H4)2F]⊖: The Structure of [K(18-Krone-6)][Si(O2C6H4)2F]
Authors: Dettlaff-Weglikowska Urszula , Hey-Hawkins Evamarie , von Schnering Hans Georg
Published: March 2015

Si(OMe)4 reacts with two equivalents of 1,2-(OH)2C6H4 in toluene at elevated temperature (70 °C) to yield a colorless microcrystalline product, which we believe to be Si(O2C6H4)2(MeOH)x (x = 1-2). [K(18-crown-6)][Si(O2C6H4)2F] has been prepared by the reaction of Si(O2C6H4)2(MeOH)x with KF and 18-crown-6 in THF and subsequent recrystallization from CH2Cl2/toluene. The title compound crystallizes orthorhombically in the space group P212121 (No. 19) with a = 10.373(1), b = 18.954(2), c = 13.993(2) Å and Z = 4. The structure was refined to a final R-value of 0.057 for 2037 reflections. The crystal structure shows the presence of close contact ion pairs [d(K –O) = 2.897(7), 2.806(8) A]. The influence of these interactions on the environment of the silicon atom is discussed and the structure of the anion compared with that of the free anion in NEt4[Si(O2C6H4)2F].
Übergangsmetallkomplexe mit Schwefelliganden, LXI / Transition Metal Complexes with Sulfur Ligands, LXI
Authors: Sellmann Dieter , Höhn Klaus , Moll Matthias
Published: March 2015

18 and 19 electron NO complexes with the [Fe'buS5'] moiety ('buS5'2- = dianion of 2,2′-bis-(2-mercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) have been isolated and converted reversibly into each other. The unpaired electron in meso-[Fe(NO)′buS5'], meso-1, is delocalized over the whole molecule and occupies an orbital that is antibonding with respect to Fe– N and Fe–S bonds. Consequently, the NO ligand is readily substituted under mild conditions. In contrast, the 18 electron complex meso-[Fe(NO)'buS5']PF6, meso-2, is entirely inert towards substitution. To our knowledge the exchange of NO by CO in meso-1 via meso-2 is the first example, in which NO is displaced by CO in an isolable NO complex. The NO release from meso-1 via meso-2 can be considered a model for reversible NO bonding in sulfur coordinated metal centres of nitrogenase. It is shown that one-electron redox reactions make stable Fe–NO bonds labile, and the reversible coordination and decoordination of NO in nitrogenase may be induced by a similar process.
Synthese und Struktur von η1-2,4-Diaza-3-phosphapenta-1,4-dien-3-yl-Komplexen des Eisens und Rutheniums / Synthesis and Structure of η1-2,4-Diaza-3-phosphapenta-1,4-dien-3-yl Complexes of Iron and Ruthenium
Authors: Weber Lothar , Sonnenberg Uwe , Stammler H. G. , Neumann Beate
Published: March 2015

The dichlorophosphido complexes (η5-C5Me5)(CO)2M–PCl2 (2a: M = Fe; 2 c: M = Ru) react with two equivalents of Ph2C=NSiMe3 to yield the first η1-2,4-diaza-3-phosphapenta-1,4-dien-3-yl complexes (4a,c). Intermediates (η5-C5Me5)(CO)2M–P(Cl)(N=CPh2) (3a,c) are detected by 31P{1H} NMR spectroscopy, the preparation of pure 3a, however, failed. The products 4a, c have been characterized by elemental analysis as well as spectroscopic data (IR, 1H, 13C, 31P NMR, MS). The molecular structure of 4a has been elucidated by single X-ray analysis.
Reaktive π-Komplexe der elektronenreichen Übergangsmetalle, 11. Mitteilung/ Reactive π-Complexes of the Electron Rich Transition Metal Complexes, Part 11
Authors: Tolxdorff Catherine , Hu Dongqi , Höferth Bernhard , Schaufele Hartmut , Pritzkow Hans , Zenneck Ulrich
Published: March 2015

The highly reactive arene iron complex [(η4-toluene)(η6-toluene)iron] allows the formation of C4-units from alkynes below room temperature. By this route butadiene-, cyclobutadiene-, and ferracyclopentadiene(arene)iron complexes are accessible. Synthesis, structure and the properties of one example each are reported. Ferracyclopentadienes are potential intermediates for the catalytic cyclotrimerization of alkynes in the coordination sphere of arene iron complexes.
Synthese und Strukturuntersuchungen von Iodocupraten(I) / Synthesis and Structure Investigations of Iodocuprates(I)
Authors: Adam Dirk , Herrschaft Bernhard , Hartl Hans
Published: March 2015

Reactions of CuI with N-methylpyrazinium iodide, (pyr)I, N-methyl-4,4′-bipyridinium iodide, (bp4)I and N-methyl-2,2′-bipyridinium iodide, (bp2)I, in organic solvents led to three novel types of copper(I) complexes of stoichiometries (pyr)Cu2I3, (bp4)Cu3I4 and (bp2)Cu2I3. In all of them the cations are n-σ-bonded to copper(I) through donation of their unshared electron pairs. (pyr)Cu2I3 crystallizes with an ionic structure (trigonal, R 3 c, hexagonal axes a = 3053(2), c = 671.9(3) pm, Z = 18). Polymeric cations ∞
1[((pyr)CuI3/3)3]3+ and anions ∞
1[CuI4/2]-form parallel rod packings. The structure motif of the cations can be described as a columnar part of the β-CuI structure in which the copper and iodine atoms are also arranged to Cu3I3 rings.

The crystal structure of (bp4)Cu3I4 (triclinic, P Ī, a = 938.8(2), b = 980.0(4), c = 1070.1(3) pm, α = 73.56(3), β = 75.79(2), γ = 89.50(3)°, Ζ = 2) is built up by uncharged chains ∞
1[(CuI4/3)(CuI3/3I1/2)((bp4)CuI2/3I1/2)]. The trinuclear units (bp4)Cu3I4 are connected via common iodide edges. The copper halide connection motif of the polymeric compound has some features in common with the “stair” and “cube” structures of adducts of CuI with unidentate, neutral P-, As- or N-bases.

The compound (bp 2)Cu2I3 (monoclinic, P 21/n, a = 1054.0(2), b = 1034.8(3), c = 1512.6(3) pm, β = 108.10(2)°, Ζ = 2) has a structure, in which two edge-sharing (CuI4/2)-tetrahedra and two approximately planar (CuI2/2(bp 2))-units form tetranuclear molecules (bp 2)2Cu4I6. These are linked to chains with a “stair” motif by intermolecular Cu ··· I contacts.
Neue 1-Aza-2 λ5, 4 λ5-diphosphirine (2 λ5, 4 λ5-Diphosphapyridine) / New 1 -Aza-2λ5, 4λ5-diphosphirines (2λ5, 4λ5-Diphosphapyridines)
Authors: Fluck Ekkehard , Spahn Manfred , Heckmann Gernot
Published: March 2015

6-(Furan-2-yl)-2,4-tetrakis(dimethylamino)-1-aza-2λ5, 4λ5-diphosphirine (2) and 6-(N-pyrrolidinyl)-2,4-tetrakis(dimethylamino)-1-aza-2λ5, 45-diphosphirine (3) were prepared by reacting 1,1,3,3-tetrakis(dimethylamino)-1 λ5,3 λ5-diphosphete with 2-cyanofuran, and N-cyanopyrrolidine, respectively. 2 and 3 are characterized by their physical properties, NMR, IR, and mass spectra. In 2 two 6J(PH) long range coupling constants could be identified.
Preparation and Properties of ω-Phosphino-phosphoniocarboxylic Acids and their Betaines
Authors: Aly Aref A. M. , Schmidbaur Hubert
Published: March 2015

In an attempt to provide phosphorus analogues of aminocarboxylic acids and their betaines, α, ω-bis(diphenylphosphino)alkanes (dppm, dppe, dppp, dppb) were converted into ω-phosphino-phosphoniocarboxylates and diphosphonio-biscarboxylates. While the reactions with haloacetic acids or haloacetates only lead to methylphosphonium derivatives owing to decarboxylation of the intermediates, β-chloropropionic acids converts Ph2P(CH2)nPPh2 compounds into the target products Ph2PCH2PPh2
+(CH2)2COOHCI- (1) and CH2[PPh2(CH2)2COOH]22Cl- (2), for n = 1. For n = 2, 3 and 4, only the analogues of 2 could be prepared (3-5). Treatment of 1 and 2 with sodium bicarbonate afforded the corresponding betaines Ph2PCH2PPh2
+CH2CH2COO- (isolated as a dihydrate 6) and CH2[PPh2
+CH2CH2COO-]2 (isolated as the tetrahydrate 7).
[Al2P4]6-, [Al2As4]6-, [Ga2P4]6- und [Ga2As4]6-, Zintl-Anionen mit 1,3-Dimethylencyclobutan-Struktur / [Al2P4]6-, [Al2As4]6-, [Ga2P4]6- and [Ga2As4]6-, Zintl Anions with 1.3-Dimethylene-cyclobutane Structure
Authors: Somer M. , Thiery D. , Peters K. , Walz L. , Hartweg M. , Popp T. , von Schnering H. G.
Published: March 2015

The compounds Cs6M2X4 (M = Al, Ga; X = P, As) were synthesized from stoichiometric mixtures of Cs, M and Cs4X6 in sealed Nb ampoules at 950 K. They are isotypic and crystallize in the monoclinic space group P21/c (No. 14) with Z = 4 formula units per unit cell. The anion partial structure is characterized by isolated [M2X4]6- units with relatively short distances for the terminal d(M–X) bonds corresponding to a Pauling Bond Order PBO = 1.5. The distances d(M–X) of the four-membered M2X2 rings correspond to single bonds.

The FIR spectra have been interpreted on the basis of the [M2X4]6- units with 2/m 2/m 2/m-D2h, symmetry by considering a factor group splitting. The assignment of the observed frequencies is supported by a normal coordinate analysis.
Zur Kenntnis von Berylliumiodat und -periodat-Röntgenographische, IR- und Raman-spektroskopische Untersuchungen / On Beryllium Iodates and Periodates - X-Ray, IR, and Raman Studies
Authors: Maneva Maria , Georgiev Mitko , Lange Norbert , Lutz Heinz Dieter
Published: March 2015

Phase relationships and thermal decomposition of beryllium iodates and periodates were studied by X-ray and spectroscopic (IR, Raman) measurements. Be(IO3)2 · 4H2O, Be(IO3)2, and Be(H4IO6)2 · 4H2O have been characterized. Be(H4IO6)2 · 4H2O (hitherto claimed in the literature to be a metaperiodate) dehydrates on heating with decomposition to form Be(IO3)2. Anhydrous beryllium periodate was not obtained. On dehydration of Be(IO3)2 · 4H2O, anhydrous Be(IO3)2 is formed, which decomposes into BeO, I2, and O2 on further heating.
Ringerweiterungs- und -verengungsreaktionen bei BN-Vier- und -Sechsringen / Expansion and Contraction Reactions with BN Four- and Six-Membered Rings
Authors: Paetzold Peter , Kiesgen Jutta , Krahé Karl , Meier Hans-Ulrich , Boese Roland
Published: March 2015

By the addition of iminoboranes RB≡NR′ (1a—d) to the corresponding diazadiboretidines (RBNR′)2 (2a—d), a ring expansion is observed, borazines (RBNR′)3 (3a—d) being formed. The particular iminoborane iPrB≡NiPr (la) can be added to the diazadiboretidines 2c—g to give borazines B3N3R2R′2iPr2 with an unsymmetrical set of ligands. From PhB=NtBu (1j) and (PhBNtBu)2 (2j), the Dewar borazine 3j′ is formed, which crystallizes in the space group P2,/c. The diazadiboretidines 2b—i, the borazines 3b—d,f, and the Dewar borazine 3e′ are split into the corresponding iminoboranes RB≡NtBu at 500-600 °C in the gas phase. The molten borazines 3b—d,f and Dewar borazines 3e′, j′ are contracted to the corresponding diazadiboretidines 2b—f, j at 160-320 °C. [Ligands R/R′: iPr/iPr (a), Me/tBu (b), Et/tBu (c), Pr/tBu (d), ¡Pr/ tBu (e), Bu/tBu (f), iBu/tBu (g), tBu/tBu (h), tBu(Me3Si)N/tBu (i), Ph/tBu (j).]
Metallorganische Verbindungen der Lanthanoide, 63 [1]. Pentalithium-okta-tert-butoxy-samarat(III): Synthese und Röntgenstrukturanalyse eines aus zwei flächenverknüpften Würfeln aufgebauten Lanthanoidclusters / Organometallic Compounds of the Lanthanoides, 63 [1]. Pentalithium Octa(tert-butoxy)samarat(III): Synthesis and X-Ray Structural Analysis of a Lanthanoid Cluster Made by Two Face Linked Cubes
Authors: Schumann Herbert , Kociok-Köhn Gabriele , Dietrich Andreas , Görlitz Frank H.
Published: March 2015

[Li(tmed)]3[Sm(CH3)6] reacts with tert-butanol in diethyl ether to give [Li5Sm(O–t-C4H9)8] (1), the structure of which has been elucidated by X-ray structure analysis. 1 crystallizes tetragonally with a = 1703(4) and c = 3178(1) pm, space group P41212, Z = 8. The structure was refined to R = 0.042 for 4082 observed reflections (Fo > 6σ(Fo)).
Das Isosterenpaar SiO/PN, I. Zur Isosterie von Perchlorcyclosiloxanen und Perchlorcyclophosphazenen. Schwingungsspektren und Röntgenstrukturanalyse von (Cl2SiO)3 und (Cl2SiO)4 / The SiO/PN Isoelectronic Pair, I. Perchlorocyclosiloxanes and Perchlorocyclophosphazenes. Vibrational Spectra and X-Ray Structure Analysis of (Cl2SiO)3 and (Cl2SiO)4
Authors: Wannagat Ulrich , Bogedain Gabriele , Schervan Adrian , Marsmann Heinrich C. , Brauer David J. , Bürger Hans , Dörrenbach Frank , Pawelke Gottfried , Krüger Carl , Claus Karl-Heinz
Published: March 2015

Hexachlorocyclotrisiloxane (2) and octachlorocyclotetrasiloxane (4) were prepared by reaction of SiCl4 with O2 at 955 °C. Their mass spectra are compared with those of the isoelectronic cyclophosphazenes. The vibrational spectra of 2 and 4 are very similar and closely related to that of (PNCl2)3, but clearly different from that of the puckered (PNCl2)4 molecule. The X-ray examination of 2 and 4 reveals planarity of the (SiO)n, n = 3 and 4 ring systems, with d(Si—O) on average 1.619(4) and 1.584(3) A, respectively.
Fluoro-, Chloro- und Bromo-Wolfram(VI)-Alkinkomplexe. Die Kristallstrukturen von [K(18-Krone-6)][WF5(Ph – C≡C – H)] · CH3CN und [WCl4(Ph – C ≡ C – Se – n – C4H9)(CH3CN)] / Fluoro-, Chloro-, and Bromo-Tungsten(VI) Alkyne Complexes. The Crystal Structures of [K(18-Crown-6)][WF5(Ph — C ≡ C — H)] · CH3CN and [WCl4(Ph — C ≡ C — Se — n — C4H9)(CH3CN)]
Authors: Neumann Petra , Dehnicke Kurt , Fenske Dieter , Baum Gerhard
Published: March 2015

Several tungsten alkyne complexes of the type [WCl4(R – C ≡ C – H)]2 and [WCl4(R – C ≡ C — R′)]2 have been prepared by reactions of WCl6 with the alkynes in the presence of C2Cl4. Treating with BrSiMe3 leads to corresponding bromo complexes, whereas reactions of NaF and KF, respectively, in acetonitrile solution in the presence of crown ethers yield the fluoro complexes [Na(15-crown-5)][WF5(R – C ≡ C – R′)] and [K(18-crown-6)][WF5(R – C ≡ C – R ′)], respectively. All complexes were characterized by IR and 13C NMR spectroscopy. The crystal structures of [K(18-crown-6)][WF5(Ph – C ≡ C – H)] · CH3CN and [WCl4(Ph – C ≡ C – Se – n – C4H9)(CH3CN)] have been determined by X-ray methods.

[K(18-crown-6)][WF5(Ph – C ≡ C – H] · CH3CN: Space group P21 Z = 2, 8555 observed unique reflections, R = 0.034. Lattice dimensions at -70 °C: a = 1199.4(3), b = 893.4(2), c = 1351.8(3) pm, β = 109.73(3)°. The compound forms ion pairs via three K – F contacts with bond lengths of 262.0, 282.7, and 293.3 pm; the potassium ion is thus nine-fold coordinated by the six oxygen atoms of the crown ether molecule and by three fluoride ligands. The alkyne ligand is bonded side on to the tungsten atom of the [WF5(Ph – Cs ≡ C – H)]- unit with WC bond lengths of 202.4 and 202.6 pm, respectively.

[WCl4(Ph – C ≡ C – Se – n – C4H9)(CH3CN)]: Space group P21/a, Z = 4,4595 observed unique reflections, R = 0.058. Lattice dimensions at -70 °C: a = 1030.3(5), b = 1596.3(9), c = 1170.9(7) pm, β = 104.28(3)°. The compound has a molecular structure, in which the tungsten atom is seven-fold coordinated by four chloride ligands, by the two alkyne carbon atoms (WC bond lengths 200 and 203 pm), and in trans position to the latter by the nitrogen atom of the acetonitrile molecule with a W – N bond length of 226 pm.
Zur Kenntnis basischer Kupferacetate / New Results on Basic Copper Acetates
Authors: Rahn-Koltermann Gudrun , Buss Dieter H. , Fuchs Robert , Glemser Oskar
Published: March 2015

Only the first three basic copper acetates of the following [Cu(CH3COO)2]2 · Cu(OH)2 · 5 H2O, Cu(CH3COO)2 · [Cu(OH)2]2, Cu(CH3COO)2 · [Cu(OH)2]3 · 2 H2O and Cu(CH3COO)2 · Cu(OH)2 · 5 H2O could be confirmed. Reproduceable directions are given. The compounds received have been characterized by powder diffraction and IR spectroscopy, the second one additionally by thermogravimetry and mass spectroscopy. A new basic copper acetate, Cu(CH3COO)2 · [Cu(OH)2]4 · 3 H2O, is described.