bluuebunny/crossref_metadata_2025 huggingface dataset:
Complexation of Poly(ethyleneimine)-Bound 8-Hydroxyquinoline with Palladium(II)
Authors: Zhou Rongnong , Geckeler Kurt E.
Published: March 2015

The complexing behavior of poly(ethyleneimine) 5-sulfonyl-8-hydroxyquinoline (POX) with palladium(II) ions in aqueous solution was studied by means of spectrophotometry in the visible region. It was shown that poly(ethyleneimine) 5-sulfonyl-8-hydroxyquinoline forms a stable, water-soluble, orange-colored complex which has a maximum absorption at a wavelength of 424 nm. The effect of pH, concentration of poly(ethyleneimine) 5-sulfonyl-8-hydroxyquinoline, concentration of palladium(II) ions, and time were investigated. The results show that in a pH range between 2 and 5, the absorbance is constant for 40 minutes. The linear concentration range for palladium(II) ions was determined to be 0-2.5 μg · ml-1 and the molar extinction coefficients 1.06 · 104 (1 · mol-1 · cm-1) for the polymeric derivative and 7.15 · 103 for the monomeric 8-hydroxyquinoline. The effect of tartaric acid as a masking agent was examined in order to eliminate the influence from other ions. The simultaneous presence of K(I), Cs(I), Li(I), Ba(II), Ca(II), Cd(II), Hg(II), Mn(II), Ni(II), Al(III), As(III), Au(III), Cr(III), Fe(III), Pt(IV), As(V) did not interfere with the complexation of poly(ethyleneimine) 5-sulfonyl-8-hydroxyquinoline and palladium(II). However, it was found that NH4
+ interferes strongly. The polymer 8-hydroxyquinoline derivative exhibited a 45% higher sensitivity to Pd(II) ions in comparison to the low-molecular-weight 8-hydroxyquinoline.
Reactions of Substituted Vinyl Cations in Acetonitrile Solution as Studied by Flash Photolysis, Part II
Authors: Kobayashi Shinjiro , Schnabel Wolfram
Published: March 2015

Vinyl cations of the structure

were generated by flash photolysis of the corresponding halides. Lifetime measurements with the aid of optical absorption measurements yielded bimolecular rate constants k2 of the reaction of I+ with tetrahydrofuran and several aliphatic alcohols. On the basis of k2 values the steric effect of various substituents R1 and R2 at C2 and the combined mesomeric (+M) and inductive (-1) effect of substituent groups at C1 on the electrophilicity of I+ have been elucidated.
NOTIZEN: Hydroxyamino Sugar Derivatives: New Glycolipid Analogs
Authors: Tronchet Jean M. J. , Cabrini Daniel , Zosimo-Landolfo Guido
Published: March 2015

Synthetic glycolipid analogs are very useful as nonionic detergents for solubilization of membrane proteins [1]. Although a large number of such detergents were described, very few ones fully satisfy the desirable properties needed for such compounds [2].
Notizen: Metallkomplexe von 3-Thiazolinen / Metal Complexes of 3-Thiazolines
Authors: Wagner Barbara , Martens Jürgen , Beck Wolfgang
Published: March 2015

The reactions of 5,5-dimethyl-3-thiazoline (L) with PdCl4
2-, PdC62-, CuCl2 and CoCl2 give the complexes ML2C12 (M = Pd, Cu, Co) and L(Cl)PdCl2Pd(Cl)L. The crystal structure of trans-PdCl2L2 has been determined by X-ray diffraction.
Darstellung, 11B-NMR- und Schwingungsspektren der closo-Hexaborate Cs2[B6H5(ONO)] und trans-Cs2[B6H4(NO2)2] / Preparation, 11Β NMR and Vibrational Spectra of the closo-Hexaborates Cs2[B6H5(ONO)] and trans-Cs2[B6H4(NO2)2]
Authors: Hake M. G. , Preetz W.
Published: March 2015

By photochemical reaction of Cs2[B6H6] with KNO2 in aqueous alkaline solution the mononitritohydrohexaborate Cs2[B6H5(ONO)] and the dinitrohydrohexaborate trans-Cs2[B6H4(NO2)2] are formed. The pure compounds have been separated by ion exchange chromatography on diethylaminoethyl cellulose. Their structures are proved by 11B NMR spectra which show the features of substituted B6 cages with C4v and D4h point symmetry. Due to the +M effect of the nitrito group in contrast to the — M effect of the nitro substituents characteristic 11B chemical shifts of opposite sign have been observed. Furthermore, the O or N coordination is distinguishable by different vibration modes within the substituents.
Die Kristallstrukturen von (PPh4)2[TiCl3(NSiMe3)]2 • CH3CN und (PPh4)2[TiCl4(OSPCl2)]2 / The Crystal Structures of (PPh4)2[TiCl3(NSiMe3)]2 · CH3CN and (PPh4)2[TiCl4(OSPCl2)]2
Authors: Wollert René , Wocadlo Sigrid , Dehnicke Kurt , Goesmann Helmut , Fenske Dieter
Published: March 2015

(PPh4)2[TiCl3(NSiMe3)]2 · CH3CN has been prepared from [TiCl2NSiMe3)]∞ with PPh4Cl in acetonitrile solution as yellow crystals. The compound crystallizes in the triclinic space group P T with one formula unit per unit cell, 3447 observed unique reflections, R = 0.053. Lattice dimensions at 200 K: a = 1030(1), b = 1253(1), c = 1374(1) pm, α = 77.46(8)°, β = 73.93(8)°, γ = 69.99(9)°. The structure consists of PPh4
+ ions and centrosymmetric dimeric anions [TiCl3(NSiMe3)]2
2-, in which pentacoordinate titanium atoms are associated via the nitrogen atoms of the silylimido groups.

(PPh4)2[TiCl4(OSPCl2)]2 has been prepared by the reaction of PPh [OSPCl2] with titanium tetrachloride in CH2C12 solution as orange crystals. (Space group P1̄, Ζ = 1, 3242 observed unique reflections, R = 0.033). Lattice dimensions at 193 K: a = 1114.8(2), b = 1190.6(2), c = 1218.7(2) pm, α = 72.18(1)°, β = 85.45(1)°, γ = 69.19(1)°. The structure consists of PPh4
+ ions and centrosymmetric dimeric anions [TiCl4(OSPCl2)]2
2-, in which hexacoordinate titanium atoms are associated via two chlorine atoms. The OSPCl2- group is coordinated via the oxygen atom.
Expedient Synthesis of Gonadotropin Releasing Hormone (GnRH) Through a Combined Chemical-Enzymatic Approach
Authors: Słomczyńska Urszula , Leplawy Tomasz , Leplawy Mirosław T.
Published: March 2015

We have developed a chemical-enzymatic synthetic approach to gonadotropin releasing hormone Glp1–His-2–Trp3–Ser4–Tyr5–Gly6–Leu7–Arg8—Pro9–Gly10–NH2 (GnRH) which enables one to perform the synthesis efficiently according to minimal protection strategy with all reactive side chains of amino acids unprotected. Five peptide bonds His2–Trp3, Tyr5–Gly6, Leu7–Arg8 and Trp3–Ser4, Ser4–Tyr5 were formed by means of a-chymotrypsin and papain, respectively. The remaining four bonds Glp1–His2, Gly6–Leu7, Arg8—Pro9, Pro9—Gly10 were formed by chemical methods. The synthesis is simple to carry out and there are no problems in scaling up as demonstrated by the final coupling on 2 g scale affording highly pure GnRH in the yield of 84-90%.
Reinvestigation of the Reaction of Arylidene Malononitrile with Cyanothioacetamide: New Approach for the Synthesis of Pyridine Derivatives
Authors: Geies A. A. , El-Dean A. M. Kamal , Monem M. I. Abdel
Published: March 2015

Arylidene malononitrile reacted with cyanothioacetamide under basic condition to afford the pyridine derivative (2). The same product was obtained from the reaction of arylidene ethylcyanoacetate, arylidene diethyl malonate, arylidene pyrazolinone with cyanothioacetamide under the same condition. A resonable mechanism for this behaviour was suggested.
Ab initio 3-21 G Calculations of Push-Pull Interactions of Substituents at Imino-Nitrogen in Formamidines. Non-Equivalence of NO-Bonds of the Nitro-Substituent
Authors: Häfelinger Günter , Krygowski Tadeusz Marek , Kuske Frank K. H.
Published: March 2015

Full ab initio 3-21 G optimization of molecular structures of twelve planar formamidines substituted by X in Ε-configuration at imino nitrogen (N2) (X = H, CH3, NH2, C6H5, OH, F, CHO, CN, BH2, NO (four isomers), NO2 (planar and perpendicular conformations), and CH2
+) yielded the following conclusions: (1) as was found earlier experimentally, an increase of the shorter CN2 bond lengths is associated linearly with a decrease of the longer CN1 bond; (2) the difference of both CN distances (Δ CN) is related linearly to the Mulliken π-electron charge density at amino nitrogen (N1); (3) a decrease of Mulliken π-charge density (Δ qπ) at N1 is linearly related to a corresponding increase of Δ qπ at N2. The scatter and a slope of –0.54 indicate a mixed mechanism of interaction between NH2 and the substituents at amino nitrogen composed of n-π-conjugation and through conjugation; (4) an increase of σ-charge density at H2 is correlated with an increase of N1 – H2 bond lengths. As a result of interaction between the lone pair at N2 and the cis-bond of the nitro substituent this bond is calculated to be significantly shorter than the other one by 0.042 A. The same effect is calculated for the E-isomer of C-nitro substituted formamidine (Δ = 0.037 A) in contrast to the corresponding Z-isomer (Δ = 0.004 Å). A selection of experimental X-ray determinations of nitro-substituted compounds confirm this effect.
Notizen: Neue Synthesewege zu Decabromodimetallaten [M2Br10]2-, M = Re, Os und Oktabromodirhenat(III), [Re2Br8]2- / New Synthesis Routes to Decabromodimetallates, [M2Br10]2-, M = Re, Os, and to Octabromodirhenate(III), [Re2Brg]2-
Authors: Hollmann P. , Preetz W.
Published: March 2015

The edge sharing bioctahedral anions [M2Br10]2-, M = Os, Re, have been prepared from [MBr6]2 in trifluoroacetic acid containing Hg2+ ions at room temperature. Heating the solid decabromodirhenate(IV) with Hg in a vacuum at 100 °C affords the octabromodirhenate(III) with a quadruple bond between the Re atoms in quantitative yields.
3,5-Diphenyl-1,2-dithiolium-hydrogensulfat – Bildung und Struktur / 3,5-Diphenyl-1,2-dithiolium Hydrogensulphate – Synthesis and Structure
Authors: Uhlemann, Erhard , Weller Frank
Published: March 2015

3,5-Diphenyl-1,2-dithiolium hydrogensulphate was prepared by the reaction of bis(thiodibenzoylmethanato)-nickel(II) with thionyl chloride in acetonitrile solution. The compound was characterized by X-ray structure determination (1261 observed, independent reflexions, R = 0,056). Crystal data: a = 543,1(1), b = 1605,7(1), c = 1678,9(2) pm; space group P 212121, Z = 4. By hydrogen bonding the hydrogensulphate ions form chains of weakly helical structure.
Synthese von Phosphaalkenclustern durch reduktive Phosphinidenfragmentierung zweizähniger Halogenphosphane RXP— CH2 — PXR mit Fe2(CO)9 / Synthesis of Phosphaalkene Clusters by Reductive Phosphinidene Fragmentation of Bidentate Halogenphosphines RXP—CH2—PXR with Fe2(CO)9
Authors: Bitterer Frank , Brauer David J. , Dörrenbach Frank , Fischer Jörg , Stelzer Othmar
Published: March 2015

Reaction of halogen functional methylenebisphosphines 1 XRP–CH2–PRX (X = Cl, Br) with excess Fe2(CO)9 affords μ3-phosphinidene clusters (5) containing phosphaalkene ligands R–P=CH2. The fragmentation of the P–C–P skeletons in 1 proceeds stepwise, phosphide complexes 2 and novel Fe3 clusters 3 with RP–CH2–PR bridging units being formed as intermediates of the oxidative addition reductive elimination process. The X-ray structural analysis for 5b (R = NEt2) reveals an Fe3(CO)9PR butterfly core to which the phosphaalkene ligand R–P=CH2 (P=C bond length 1.766(4) A) is coordinated in a μ3,η2-manner. In case of methylenebisphosphines 1 with bulky substituents (R = 2,4,6-iPr3C6H2) the phosphinidene fragmentation of the P–C–P skeleton is accompanied by the formation of 2,3-dihydrobenzo[b]-phosphole ligands.
Unendliche Y2(H2O)10[C6(COO)6]-Ketten in Y2[C6(COO)6] · 14H2O / Infinite Chains of Y2(H2O)10[C6(COO)6] in Y2[C6(COO)6] · 14 H2O
Authors: Robl Christian , Hentschel Stephanie
Published: March 2015

Colourless monoclinic single crystals of Y2[C6(COO)6]· 14H2O were grown in aqueous silica gel (space group P21/n, a = 847.5(1), b = 923.4(2), c = 1632.0(3) pm, β = 100.33(1)°, Ζ = 2, 223 parameters, 1784 reflections, Rg = 0.0357). Y3+ is coordinated by 5 water molecules and 3 oxygen atoms of the mellitate anion in a dodecahedral fashion. Y3+ and [C6(COO)6]6- ions are linked by coordinative bonds, yielding infinite chains of composition Y2(H2O)10[C6(COO)6] extending parallel to [100]. Hydrogen bonds connect adjacent chains.
Crystal and Molecular Structure and Properties of Tetrasodium
[Bis { (µ-isothiocyanato-N,S)(N-salicylidene-β-alaninato) } dicuprate(II)] Dithiocyanate Tetrahydrate
Authors: Kettmann V. , Krätsmár-Šmogrovič J. , Švajlenová O. , Žemlička M.
Published: March 2015

The binuclear antiferromagnetically superexchange-coupled aquabis(N-salicylidene-β-alaninato)dicopper(II) monohydrate reacts with NaSCN to yield a complex cuprate(II) of stoichiometry Na2Cu(sal-β-ala)(NCS)2 · 2 H2O. The compound has a magnetic moment μ/eff = 1.85. μΒ (Τ = 295 K), and an axial EPR spectrum with g11 > g⊥.

The crystal and molecular structure of the title compound has been determined and refined to R = 0.055 (Rw = 0.062) for 1535 observed reflections, [I > 2σ(I)]. The crystals are triclinic, space group P1̅, with cell dimensions: a = 6.989(3), b = 10.445(5), c = 12.692(6)Å; α = 84.88(5), β = 70.13(4), and γ = 86.72(6)°, V = 869 Å3; Z = 2. The coordination environment of the Cu(II) atom is axially distorted square pyramidal (4 + 1). The basal plane of the pyramid is formed by the 01, Ν 1, and O 2 donor atoms of the tridentate sal-β-ala(2—) Schiff base ligand and by the N 2 atom of the additional NCS(1—) ligand. The apex of the pyramid is occupied by the weakly contacting S l′ atom of the bridging —NCS— ligand, Cu—S 1′ = 2.933(2) Å, thereby giving rise to [Cu2(sal-β-ala)2(μ-NCS)2]2- centrosymmetric binuclear complex anion. The remaining components of the crystal structure are SCN- (uncoordinated to Cu2+), Na+ ions, and H2O molecules.
Struktur von Ferribactin aus Pseudomonas fluorescens ATCC 13525 [1] / The Structure of Ferribactin from Pseudomonasfluorescens ATCC 13525 [1]
Authors: Hohlneicher U. , Hartmann R. , Taraz K. , Budzikiewicz H.
Published: March 2015

The primary structure of deferriferribactin 13525 which is produced by Pseudomonas fluorescens ATCC 13525 under iron deficient conditions was elucidated by 2 D-NMR-spectroscopic methods.
Notizen: Synthese und Kristallstruktur von [{(CO)5CrPhP}2Se3] / Synthesis and Crystal Structure of [{(CO)5CrPhP}2Se3]
Authors: Merzweiler Kurt , Kersten Hans-Jörg
Published: March 2015

The reaction of [{(CO)5Cr}PhPCl2] with Se(SiMe3)2 leads to the formation of [{(CO)5CrPhP}2Se3] (1). 1 contains a P2Se3-heterocycle which is coordinated to two {(CO)5Cr} units. 1 was characterized by NMR spectroscopy (31P, 77Se) and single crystal X-ray diffraction.
Kristallstruktur und Schwingungsspektren von Li5CrCl8 / Crystal Structure and Vibrational Spectra of Li5CrCl8
Authors: Lutz Heinz Dieter , Kuske Peter , Pfitzner Arno , Steiner Hermann-Josef
Published: March 2015

The crystal structure of the novel pink Li5CrCl8 oC28 has been determined by both single crystal X-ray and neutron powder studies. The title compound crystallizes in a hitherto unknown structure type (space group C mmm, Z = 2). The final R values are R = 3.4% (715 independent reflections with I > 3aI) and Rwp = 11.5%, respectively (a = 1019.79(3), b = 723.94(2) and c = 726.16(3) pm). The structure consists of edge-connected Li(l)Cl6 and alternating edge-connected Li(2)Cl6 and CrCl6 octahedra, respectively. It is related to the NaCl super structure SnMn2S4 type. IR and Raman spectra as well as symmetry coordinates are given and discussed in terms of CrCl6 and LiCl6 breathing modes.
Polysulfonylamine, XXXVI Trimethylsilyl-dimesylamin: Darstellung, NMR-spektroskopische Charakterisierung und Reaktionsfähigkeit als Silylierungsreagens / Polysulfonylamines, XXXVI Trimethylsilyl Dimesylamine: Preparation, NMR-Spectroscopic Characterization, and Reactivity as a Silylating Agent
Authors: Blaschette Armand , Wieland Elke , Hamann Thomas , Harris Robin K.
Published: March 2015

(CH3)3SiN(SO2CH3)2 (1), m. p. 69-70 °C, is obtained by metathesis of AgN(SO2CH3)2 with (CH3)3SiCl (improvement of a known procedure) or, more conveniently, by silylation of HN(SO2CH3)2 with [(CH3)3Si]2NH. The 1H, 13C and 29Si NMR solution spectra and the 29Si NMR solid-state spectrum suggest the constitution of 1 in solution (CDC13, CD2C12, CDCl2–CDCl2) to be an equilibrium mixture of the N-silylated form (CH3)3Si–N(SO2CH3)2 (I) and the O-silylated form (CH3)3Si–O–S(O)(CH3)=NSO2CH3 (II) in a molar ratio of 2:1 at room temperature, whereas in the known crystal structure of 1 only form I is present. The solid-state NMR experiment acted as a bridge between X-ray crystallography and solution-state NMR, enabling assignments of the resonances to be made with confidence to the tautomers. At room temperature, form II undergoes a rapid intramolecular 1.5-migration of silicon between oxygen centers of the two sulfonyl groups. As shown by kinetic measurements using 1H NMR spectroscopy, 1 is a highly reactive agent for silylating ketones in the presence of triethylamine. Hydroxy and thiol functions, even when sterically hindered, are silylated by 1 in uncatalyzed reactions. It is further shown that HN(SO2CH3)2 is an efficient catalyst for silylations with [(CH3)3Si]2NH.
Template Synthesis of Co(II) Complexes of Tetraazamacrocycles
Authors: Rai Pramod K. , Gupta Ajay K. , Prasad Raghu N.
Published: March 2015

2+2 Cyclocondensation of benzil with aliphatic diamines viz. 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane or 1,12-diaminododecane in the presence of Co(II) as a template yields a series of pentacoordinated high spin Co(II) complexes of the type [CoLX]X (where L = N4 macrocycle having 12- to 32-membered ring and X = NO3, Cl). The complexes have been characterized by elemental analyses, IR and diffuse reflectance spectra, conductances and magnetic measurements.
Substituenteneinflüsse auf Synthese und Eigenschaften von Hexakis[phosphanaurio(I)]methanium(2+)bis(tetrafluoroboraten) / Substituent Effects in Synthesis and Properties of Hexakis[phosphineaurio(I)]methanium(2 +) Bis(tetrafluoroborates)
Authors: Schmidbaur Hubert , Brachthäuser Benno , Gamper Siegfried , Schier Annette , Steigelmann Oliver
Published: March 2015

Polyaurated carbon complexes of the type [(L–Au)6C]2+ with functionalized phosphine ligands have been prepared by the reaction of the phosphinegold(I) chlorides R(Ph)2PAuCl (R = p-C6H4-Cl 2a,p-C6H4-Br 2b,p-C6H4-CH3 2c,p-C6H4-OCH3 2d,p-C6H4-COOH 2e, p-C6H4–N(CH3)2 2f), R2(Ph)PAuCl (R = p-C6H4-N(CH3)2 2g) and R3PAuCl (R = p-C6H4-N(CH3)2 2h) with tetrakis(dimethoxyboryl)methane in HMPT at room temperature. Clearly depending on the different inductive and mesomeric effects, the preparation of the clusters with substituents like –CH3 3c, –OCH3 3d and –N(CH3)2 3f needs shorter reaction times and the products show better solubility in organic solvents than those with functional groups like –Cl 3a, –Br 3b and –COOH 3e. The 31P magnetic resonance parameters are correlated with electronic effects of the substituents, but the chemical shift of the interstitial carbon atom in the 13C-NMR spectra is largely independent of the coordinating ligands. For the phosphinegold(I) chlorides 2f–h X-ray structure analyses have been performed.
119Sn NMR Spectroscopy of Some Iron-Tin Compounds – First Measurements of One-Bond Coupling Constants 1J(119Sn57Fe), Geminal Coupling Constants 2J(119SnFe119Sn) and the Dependence of 119Sn Chemical Shifts on the Nature of the Sn–Fe Bond
Authors: Wrackmeyer Bernd , Distler Berthold , Herberhold Max
Published: March 2015

Carbonyliron tin complexes CpFe(CO)2–SnMe3 (1), cis-(CO)4Fe(SnMe3)2 (2), cis-(CO)4Fe(SnMe2Cl)2 (3), [R2SnFe(CO)4]2 (4a, R = Me; 4b, R = Bu), {Me2Sn[Fe(CO)4]2}2Sn (5), Me2Sn[Fe(CO)4]2Sn[Fe(CO)4]2 (6) and Sn[Fe(CO)4]4 (7) were studied by 119Sn NMR. It proved possible for the first time to observe coupling constants 1J(119Sn57Fe) in the range of 36 to 64 Hz. The large magnitude of geminal coupling constants |2J(119SnFe119Sn)| (1400 to 1800 Hz) in the cyclic compounds 4 to 6 indicates the presence of tin-tin interactions as an efficient coupling pathway. Extreme deshielding of 119Sn nuclei in the complexes 6 (δ119Sn + 953) and 7 (δ119Sn + 1532) is associated with three-centre FeSnFe bonds in these compounds.
Cycloadditionen, XX Thermisch induzierte intramolekulare Reaktionen bei 2-Methyl-2,3-butadienamiden / Cycloadditions, XX Thermally Induced Intramolecular Reactions of 2-Methyl-2,3-butadienamides
Authors: Himbert Gerhard , Schlindwein Hans-Jürgen
Published: March 2015

The 2-methyl-2,3-butadienamides 4a—m are directly synthesized by the reaction of the corresponding allenic acid chloride 2 with the secondary amines 3. At heating, 4a—j undergo the intramolecular Diels-Alder reaction, by using their ω-standing double bond and the π-system of the directly bonded phenyl groups or of the “methylenic” bonded arenes or furans. Thereby the tricycles 6a—g (bearing five-membered lactam moreties) and/or the tricycles 7-9 (bearing six-membered lactam moreties) are formed. The influence of the geminai methyl group on the chemoselectivity and on the velocity of the IMDA reactions is investigated. The N-allyl derivatives of 4 (s. 41 and m) form the bicycles 10 by intramolecular [2+2]-Cycloaddition.
Synthese und Kristallstruktur von Bromotriphenylphosphoniumtribromid, [(C6H5)3PBr]Br3 / Synthesis and Crystal Structure of Bromotriphenylphosphonium Tribromide, [(C6H5)3PBr]Br3
Authors: Vogt H. , Trojanov S. I. , Rybakov V. B.
Published: March 2015

Bromotriphenylphosphonium tribromide, [(C6H5)3PBr]Br3, has been prepared by the reaction of triphenylphosphine with bromine in dichloromethane. Light-brown crystals are obtained by recrystallization from the same solvent.

The crystal and molecular structure of the title compound has been determined. The crystals are monoclinic, space group P21/c, Z = 8; a = 1917.1(8), b = 1182.2(9), c = 1823.5(4) pm, β = 108.34(2)°. R = 0.056 (Rw = 0.063) for 1813 reflections with I ≥ 3σ(I). In the solid state the title compound exists as discrete monomeric (C6H5)3PBr+ and Br3⁻ ions with two crystallographically independent ions of each sort. The cations have a slightly irregular tetrahedral geometry around the P atom. The tribromide anions are nearly symmetrical and slightly bent.
Alkalisilanolate und -siloxanolate als Precursor für Si–O-Ringe / Alkali Silanolates and Siloxanolates as Precursors for Si–O Rings
Authors: Schütte Steffen , Klingebiel Uwe , Schmidt-Base Dieter
Published: March 2015

The disilanol (CMe3)2Si(OH)2 (1) serves as a starting material in the reaction with C4H9Li and sodium for the construction of the alkali derivatives 2,3,4, and the siloxanes 5,6,7,8. The six-membered cyclosiloxane 10 and the spirocyclic compound 11 are easily prepared in the reaction of [(Me3C)2Si(OH)]2O (8) with 2C4H9Li and SiF4 or SnBr4. The crystal structures of (Me3C)2Si(OLi)2 (3), (Me3C)2Si(ONa)OH (4), and (Me3C)2Si(ONa)OSiF(Me3C)2 (9) have been determined and are discussed.
Darstellung und Charakterisierung von Kupfer(II)-Derivaten des Glycyll-β-alanins und des β-Alanylglycins. Kristallstruktur von Cu(II)-ßAlaGly • H2O / Preparation and Characterization of Copper(II) Derivatives of Glycyl-β-alanine and β-Alanylglycine. Crystal Structure of Cu(II)-β-AlaGly • H2O
Authors: Schmiedgen Ralf , Huber Friedo , Preut Hans
Published: March 2015

Aquacopper(II) glycyl-β-alaninate (1) and aquacopper(II)-β-alanylglycinate (2) were obtained from CuCO3 and the appropriate dipeptide under reflux in water. 2 crystallizes in the orthorhombic space group Pna2I. The lattice constants (291 K) are: a = 8.984(2), b = 12.456(2), c = 6.978(2) Å. The dipeptide anion, acting as a tridentate ONN ligand, and one oxygen atom of the carboxylate group of a neighbouring molecule form the base of a square pyramid around Cu, with water in the apical position. Cu is found slightly above the base. The molecules are connected by bridging carboxylate groups to form chains which are linked by hydrogen bonds between the water molecule and the oxygen atom of the peptide group.
1-[4- { 1,1′,1″,1‴-(1,3-Cyclopentadien-1,2,3,4-tetrayl)tetrakis} ]-(4,1-phenylen)-alkanone und deren Natrium-, Thallium(I)- und Fe(II)-Komplexe / 1-[4- { 1,1′,1″,1‴-(1,3-Cyclopentadiene-1,2,3,4-tetrayl)tetrakis} ](4,1 -phenylene)-alkanones and their Sodium, Thallium(I) and Iron(II) Complexes
Authors: Schumann Herbert , Kucht Andreas , Kucht Homa , Lentz Alexander , Esser Lothar , Weimann Roman
Published: March 2015

Tetraphenylcyclopentadiene (1) reacts with acylchlorides RC(O)Cl (R = CH3, C3H7, C5H11,C7H15) to form the corresponding [(cyclopentadiene tetrayl)tetrakis] (4,1-phenylene)alkanones C5H2(C6H4C(O)R-4)4 (2a, 2b, 2c and 2d). 2a reacts with NaNH2 generating the corresponding sodium salt Na[C5H(C6H4C(O)R-4)4] (3a). 2a, 2b, 2c, and 2d react with T1OC2H5 yielding the thallium(I) derivatives Tl[C5H(C6H4C(O)R-4)4] (4a, 4b, 4c, 4d). Octaphenylferrocene (5) reacts with acylchlorides RC(O)Cl (R = CH3, C3H7, C5H11, C7H15) to form octaacylated ferrocenes Fe[C5H(C6H4C(O)R-4)4]2 (6a, 6b, 6c and 6d). 6a can also be prepared by reacting FeI2 with 3a. 6a reacts with NaOBr yielding Fe[C5H(C6H4C(O)OH-4)4]2 (7), which after reaction with C5H11OH and C7H15OH gives the corresponding octaesters Fe[C5H(C6H4C(O)OR-4)4]2 (8c and 8d). 6a and 6b are reduced by N2H4(H2O) to give Fe[C5H(C6H4CH2R-4)4]2 (11a and 11b). The X-ray crystal structures of tetraphenylcyclopentadiene (2 a), as well as of the partially and totally substituted ferrocene derivatives Fe[C5H(C6H4C(O)CH3-4)4][C5H(C6H4C(O)CH3-4)3(C6H5)] (9), Fe[C5H(C6H4C(O)C3H7-4)(C6H5)3]2 (10) and Fe[C5H(C6H4C4H9-4)4]2 (11b) have been determined. The 1H and 13C NMR spectra of the new compounds are reported and discussed.
Structure and Magnetic Properties of a (μ-Oxo)diiron(III) Complex
Authors: Elmali Ayhan , Elerman Yalcin , Svoboda Ingrid , Fuess Hartmut , Griesar Klaus , Haase Wolfgang
Published: March 2015

μ-Oxo-bis[N ,N '-o-phenylene-di(salicylaldiminato)iron(III)] was synthesized in dioxane solvent and its crystal structure determined. [C2OH14N ,OiFe]-,O · (C4H8O2), monoclinic, space group P21/ c ,a = 14.650(2), b = 18.990(1), c = 13.296(1) Å, β = 76.080(7), V = 3590.3 Å3, Z = 4. Two iron (III) atoms in square pyramidal pentacoordination are bridged by an oxygen atom with an Fe - O - Fe angle of 145 and a Fe-Fe distance of 3.409(1) Å. The iron (III) centers are antiferrommagnetically coupled (J = -9 8 .5 cm-1), as derived from temperature-dependent magnetic susceptibility measurements in the range 4.2 to 286.5 K.
Biomimetische Photosysteme zur sakrifiziellen Wasserreduktion / Novel Biomimetic Systems for Visible Light Induced Water Reduction
Authors: Boßmann Stefan , Dürr Heinz , Mayer Eduard
Published: March 2015

Novel microheterogeneous systems for the direct photoreduction of water using visible light in analogy to the photochemical reaction center of Rhodopseudomonas viridis are described in detail. These physical model systems for photosynthesis feature the recently synthesized bisheteroleptic metal complexes [Ru(bpy)2(PP)]Cl2, [Ru(bpy)2(PPB)]Cl2, [Ru(bpy)2(PPB-pCl)]Cl2 and [Ru(bpy)3]Cl2, adsorbed on a negatively charged SiO2—TiO2-colloid, the zwitterionic electron relay PVS and a long-term stable and highly efficient TiO2—Pt-“antenna” catalyst as well as TEOA as sacrificial electron donor.

Evidence for the directed absorption of the sensitizers on the SiO2—TiO2-colloid is taken from UV-VIS-measurements, steady-state luminescence-spectroscopy and the quantum yields for PVS-reduction.

The hydrogen production in the presence of the SiO2—TiO2-colloid is clearly enhanced and proofs the validity of the underlying concept of physical model systems for photosynthesis.
Notizen: The Bishydridobis(tetrazol-1-yl)borate Anion, [H2B(CHN4)2]-: Synthesis and Structure of the First Tetrazolylborate
Authors: Janiak Christoph , Esser Lothar
Published: March 2015

Potassium bishydridobis(tetrazol-1-yl)borate (1) has been synthesized from KBH4 and tetrazole and characterized spectroscopically. Its crystal structure has been determined. 1 crystallizes in the monoclinic space group P21/n with a = 537.8(2), b = 1703.5(9), c = 919.6(3) pm, β = 106.12(3)° and V = 809.4(6)· 106 pm3.
Notizen: Photoredox Reaction of [Hg(cyclam)]2+[Co(CO)4]⁻ Induced by Outer Sphere Charge Transfer Excitation
Authors: Kunkely Horst , Vogler Arnd
Published: March 2015

The ion pair [Hg(cyclam)]2+[Co(CO)4]- displays a Co(–I) to Hg(II) metal-to-metal charge transfer (MMCT) band at 288 nm. Upon MMCT excitation the ion pair undergoes a photoconversion to [HgCO2(CO)8].
Untersuchungen an Polyhalogeniden, XII [1] Darstellung und Kristallstruktur von [K(Crypt-2.2.2)]l2I12 / Studies on Polyhalides, XII [1] / Preparation and Crystal Structure of [K(Crypt-2.2.2)]2I12
Authors: Tebbe Karl-Friedrich , Kavoosian Arista
Published: March 2015

The new compound [K(Crypt-2.2.2)]2I12 has been prepared by the reaction of [K(Crypt-2.2.2)]I with iodine in a mixture of ethanol and dichloromethane. It crystallizes in the triclinic space group PĪ with a = 1201,5(5), b = 1213,4(5), c = 1432,1(2) pm, α = 69,11(2), β = 72,01(2), γ= 61,93(3) and Z = 1. The crystal structure has been refined to RF = 0.030 for 2882 reflections. The structure may be described as a layerlike packing of I12
2- anions and [K(Crypt-2.2.2)]+ cations. The anion with point symmetry Ci consists of two pentaiodide groups and a bridging iodine molecule.
Titrimetrische Analyse von Ionenaustauschgleichgewichten bei Unvollständigkeit der Titrationskurven / Titrimetric Analysis of Ion-Exchange Equilibria in the Case of Incomplete Titration Curves
Authors: Hilgers Uwe , Blume Rüdiger
Published: March 2015

A method is described which allows the titrimetric determination of the pH of decomplexation and of the formation constant of chelating ion-exchangers, although the titration curve is not complete. Iterative linearization leads to the formation constants and allows the completion of the titration curves. The studied systems are of the type MeL and MeL2, where the metals Me are zinc, copper and manganese, and the ligand L is Eriochrome Black T. The method may also be used for the determination of the number of ligands in a complex of the type MeLn.
pH-Dependent Tautomerism and pKa Values of Phloroglucinol (1,3,5-Trihydroxybenzene), Studied by 13C NMR and UV Spectroscopy
Authors: Wang Degui , Hildenbrand Knut , Leitich Johannes , Schuchmann Heinz-Peter , Sonntag Clemens von
Published: March 2015

13C NMR and UV spectroscopy of aqueous phloroglucinol over the pH range 2.6 to 15 confirms that the dianion exists predominantly as the keto form (3,5-dihydroxy-2,5-cyclohexadienone dianion 2c, δ(>CH2) = 46 ppm, δ(≥CH) = 101 ppm, δ(C3,C5) = 188 ppm, δ(C1) = 197 ppm). All other states of ionization, i.e. neutral la (δ(>CH) = 98 ppm, δ(5(C1,C3,C5) = 160.9 ppm), monoanion 1b (δ(>CH) = 98 ppm, δ(C1,C3,C5) = 164.4 ppm) and trianion 1d (δ(>CH) = 100 ppm, δ(C1,C3,C5) = 170 ppm) exist predominantly as the benzene forms. There is some evidence, consisting of a broadening of the signals from the 3,5-dihydroxy-2,5-cyclohexadienone dianion 2c in the pH range from ∾ 9 where they start to appear, to ∾10 where they approach their maximum values, for a small but noticeable equilibrium concentration of the cyclohexen-1-ol-3,5-dione (monoanion) 3b or the 3,5-dihydroxy-2,5-cyclohexadienone (monoanion) 2b forms. Other keto forms have not been detected. The third pKa turns out to be close to 14.
Aziridines, 61. Ring Opening of 2,2-Dimethyl-l-sulfonylaziridines by Anilines: Regioselectivity and Revised Structure of Main Products
Authors: Buchholz Berthold , Lin Pen-Yuan , Onistschenko Andreas , Stamm Helmut
Published: March 2015

It is shown (1) that in most reactions of anilines 2 with 1-sulfonyl-2,2-dimethylaziridines 1 both isomeric products 3 and 4 are formed, (2) that the “normal” product 4 obtained by attack on position 3 of 1 usually arises in a small or negligible amount that seems to decrease with decreasing basicity of 2, and (3) that the amount of 4 strongly increases with increasing steric demand of 2. Formation of 4 is explained by a lag of bond making in SN2.
Synthesis of 4-Cyanofuro(2,3-b)quinolines
Authors: Rajamanickam P. , Shanmugam P.
Published: March 2015

Synthesis of 4-cyanofuro(2,3-b)quinolines starting from 2-chloro-4-cyano-3-vinylquinolines is described.
Chalcogeno-substituierte Triphenylmethylium-Ionen vom inversen Malachitgrün-Typ / Chalcogeno-Substituted Bis-triphenylmethylium Ions of the Inverse Malachite Green Type
Authors: Hellwinkel Dieter , Stahl Heinz
Published: March 2015

The longest wavelength VIS absorptions of the deeply colored CF3CO,H solutions of the 4,4′-chalcogenobis-(triphenylmethylium) ions 4++, Y[C6H4C(C6H5)2]2 (Y = O,S,Se,Te) resemble closely those of the corresponding monocationic 4-arylchalcogenotriphenylmethylium systems 5+, ArYC6H4C(C6H5)2, and not those of the structurally directly related 4,4′-bis(arylchalcogeno)triphenylmethylium ions 3+, C6H5C(C6H4YAr)2. This is in striking contrast to the results obtained previously for analogous nitrogen systems, where “inverse”, 2++, RN[C6H4C(C6H5)2], and “conventional” malachite green systems 1+, (Ar2NC6H4)2CR, yield almost indentical Amax values. A rationalization of these observations can be achieved based on the assumption of largely delocalized dications 2++ versus more or less orthogonal “double monocationic” systems 4B++ separated due to torsional twist. Whereas the formal push-pull systems 6+, ArSC6H4YC6H4C(C6H5)2 (Y = O,S,Se) behaved practically like the corresponding standard systems 5+, the mono- and bis-triphenylmethylio-substituted dibenzofurane, dibenzothiophene and thioxanthene derivatives 8+, 9++, 10+ and 11++ displayed hypsocromic shifts of their color bands relative to their noncyclic analogues which are only partly in accordance with predictions based on a simple frontier orbital Hückel model. The 1H and 13C NMR spectra of all these cationic species comply with their respective charges.
Notizen: Photocatalytic 1,4-Hydrosilation of 1,3-Butadiene with Triethylsilane
Authors: Abdelqader Wafa , Özkar Saim , Peynircioǧlu N. Bekir
Published: March 2015

Chromium and molybdenum carbonyl photocatalyzed hydrosilation of 1,3-butadiene by triethylsilane yields exclusively the 1,4-adduct, cis-l-triethylsilyl-2-butene which has been fully characterized. Mechanistic possibilities for photocatalytic hydrosilation reactions have been put forward.
Notizen: Darstellung und Kristallstruktur von [{(CO)5WPhP}2S2] / Synthesis and Crystal Structure of [{(CO)5WPhP}2S2]
Authors: Merzweiler Kurt , Kersten Hans-Jörg
Published: March 2015

The reaction of [{(CO)5W}PhPCl2] with S(SiMe3)2 leads to the formation of [{(CO)5WPhP}2S2] (1). 1 crystallizes in the space group P21/n. The lattice constants (at 298 K) are: a = 658.9(3), b = 2287.6(11), c = 1905.5(9) pm, β = 94.53(3)°. According to the crystal structure determination 1 contains a four-membered P2S2 ring which is coordinated to two {(CO)5W} units.
Addukte Aromat/Chlorwasserstoff bei tiefen Temperaturen: Beiträge zu Bildung und Kristallstruktur [1] / Adducts Arene/Hydrogen Chloride at Low Temperatures: Contributions to Formation and Crystal Structure [1]
Authors: Deeg Axel , Mootz Dietrich
Published: March 2015

The melting diagrams of the systems benzene-HCl, toluene-HCl and mesitylene-HCl have been established and the crystal structures of two adducts determined. The adduct toluene · 2 HCl, melting incongruently at -115°C, is monoclinic with space group C2/c and Ζ = 4 formula units per unit cell; the adduct mesitylene · HCl, m. p. -64°C, is orthorhombic with space group Pbca and Ζ = 8. The HCl molecules are situated on both sides and one side, respectively, of the plane of the aromatic system and are linked to it by weak hydrogen bonds of the type Cl-H···π.
Koordinationschemie perhalogenierter Cyclopentadiene und Alkine, XI [1].
Darstellung einiger Cymantrenyl-mono- und bis-thioether mit einer weiteren funktionellen Gruppe am Cyclopentadienylring. Molekülstruktur von [C5Cl2(SMe)2(PPh2)]Mn(CO)3 / Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, XI [1]
Synthesis of Some Cymantrene Mono- and Bis-Thioethers with One Additional Functional Group on the Cyclopentadienyl Ring. Molecular Structure of [C5Cl2(SMe)2(PPh2)]Mn(CO)3
Authors: Sünkel Karlheinz , Blum Adrian , Wagner Barbara
Published: March 2015

Chiral Cyclopentadienyl Complexes, Crystal Structure

The reaction of [C5Cl4(SMe)]Mn(CO)3 (la) with n-butyllithium and the electrophiles SiMe3Cl, CO2, or PPh2Cl regiospecifically yields the chiral 1,3-disubstituted functional cymantrene thioethers [C5Cl3(SMe)R]Mn(CO)3 (R = SiMe3 (2), COOLi (3a), PPh2 (4)). 3 a can be protonated to give the corresponding carboxylic acid (3b), which in turn can be transformed to the acid chloride [C5Cl3(SMe)(COCl)]Mn(CO)3 (3c). 3c reacts with NaN3 to yield after work-up the urea derivative OC[[NH—C5Cl3(SMe)]Mn(CO)3]2 (3d). Using the cymantrene bisthioethers [C5Cl3(SR)2]Mn(CO)3 (R = Me, 5a, Ph, 5b) as starting materials, the carboxyl derivatives [C5Cl2(SMe)2(COR)]Mn(CO)3 (R = OLi, 6a, OH, 6b, Cl, 6c) and the potential organometallic S,P-chelate ligands [C5Cl2(SR)2(PPh2)]Mn(CO)3 (R = Me, 7a, Ph, 7b) can be obtained. The crystal structure determination of 7a (C22H16O3PS2Cl2Mn, monoclinic, P 21/c, a = 18.714(6) A, b = 9.506(3) A, c = 14.475(3) Α, β = 109.18(2)°, V = 2432.1(12) Α3, Z = 4) shows an orientation of the neighbouring PPh2- and SMe groups, that allows chelation of an additional metal fragment.
Darstellung, 11B-, 13C-NMR- und Schwingungsspektren der closo-Hexaborate [B6H5(CN)12- und cis-[B6H4(CN)2]2− sowie Kristallstruktur von Cs2[B6H5(CN)] / Preparation, 11B,13C NMR and Vibrational Spectra of the closo-Hexaborates [B6H5(CN)]2- and cis-[B6H4(CN)2]2-, and the Crystal Structure of Cs2[B6H5(CN)]
Authors: Preetz W. , Franken A. , Rath M.
Published: March 2015

By reaction of Cs2[B6H6] with in situ generated dicyanogen in aqueous alkaline solution the monocyanohydrohexaborate Cs2[B6H5(CN)] and the dicyanohydrohexaborate cis-Cs2[B6H4(CN)2] are formed. The compounds have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of Cs2[B6H5(CN)] was determined from single crystal X-ray diffraction analysis; monoclinic, space group P21/a with a = 9.540(8), b = 9.977(3), c = 10.578(2)Å, β = 105.06(2)°. The B6 octahedron is compressed in the direction of the nearly linear B—CN bond by about 5%, with bond lengths between 1.71 and 1.76Å. The "B NMR spectra of the two compounds reveal the features of substituted B6 cages with C4v and C2v point symmetry. In the 13C NMR spectrum of Cs2[B6H5(CN)] a quartet at -139 ppm with 1J(C,B) 92 Hz is observed. The IR and Raman spectra exhibit very strong CN stretching bands for Cs2[B6H5(CN)] at 2149, and for cis-Cs2[B6H4(CN)2] at 2170 cm-1.
Metallkomplexe mit funktionalisierten Schwefelliganden, V Ruthenium(II)-Alkyl- und -Arylthiosulfinato-Komplexe. Kristallstrukturanalyse von CpRu(PPh3)(CO)[S-S(O)-CH2-C6H5] / Metal Complexes of Functionalized Sulfur Containing Ligands, V Ruthenium(II)-Alkyl-and -Arylthiosulfinato Complexes. X-Ray Structure Determination of CpRu(PPh3)(CO)[S-S(O)-CH2-C6H5]
Authors: Weigand Wolfgang , Bosl Gabriele , Robl Christian , Kroner Jürgen
Published: March 2015

Compounds of the type CpRu(PPh3)(L)(SH) [L = PPh3 (2), CO (4)] react with N-alkyl and -arylsulfinyl phthalimides 3a-f to give the chiral complexes CpRu(PPh3)(L)[S-S(O)-R] (L = PPh3, 5a: R = C4H9,5b: R = C12H25,5d: R = C18H37,5e: R = Tol; L = CO, 6a: R = C4H9,6b: R = C12H25,6c: R = C16H33,6d: R = C18H37,6f: R = CH2Ph). With 6a-c diastereoselectivities of 5:2, with 6d 5:1, and with 6f 10:3, respectively, are observed. The compounds 5,6 are characterized by their spectroscopic data; the X-ray structural determination of u-6f shows a sulfur-sulfur bond length of 208,6 (3) pm, the dihedral angle Ru-S(1)-S(2)-C(25) is 170,8°. Extended Hückel calculations give information about the rotational barrier around the S-S(O) axis.
Fünffach koordinierte Co(III)-Komplexe [Tripod-Cobalt-(ortho(X)(Y)C6H4)]+ mit ortho-phenylenverbrückten Chelatliganden [(XH)(YH)C6H4] (XH, YH = NH2, OH, SH) / Five-Coordinate Co(III) Complexes [Tripod-Cobalt-(ortho-(X)(Y)C6H4)]+ Containing ortho-Phenylene-Bridged Chelate Ligands [(XH)(YH)C6H4] (XH, YH = NH2, OH, SH)
Authors: Vogel Sabine , Huttner Gottfried , Zsolnai Laszlo
Published: March 2015

The ortho-phenylene compounds ortho-[(XH)(YH)C6H4] (XH, YH = NH2, SH, OH) react with Co(BF4)2•6H2O and Tripod (CH3C(CH2PPh2)3) to give the five-coordinate Co(III) complexes [Tripod-Cobalt-(ortho-(X)(Y)C6H4)]+ (X, Y = NH, O, S), 1-6.

The structures of 1—6 have been characterized by X-ray analyses of appropriate salts. The compounds have further been characterized by IR, NMR, UV-VIS and cyclovoltammetric measurements.

As a compound analogous to 1—6, but containing the saturated chelate ligand [(S)C2H4(S)]2- instead of the conjugated ortho-phenylene type ligands of 1-6, [Tripod-Cobalt-((S)C2H4(S))]+, 7, has been prepared and fully characterized. It is inferred that the coordination geometries of 1-7 do not strongly depend on conjugative interaction within the chelating ligands.
Juglorubin
Authors: Lessmann Holger , Krupa Johann , Lackner Helmut , Schmidt-Bäse Karen , Sheldrick George M.
Published: March 2015

The isolation of Juglorubin (2) from cultures of Streptomyces spp., which produce a series of other hydroxynaphthoquinones, is described. 2 is a unique, unusually condensed ionic colorant with the formula C28H17NaO11. The structure of 2 was elucidated by X-ray structure analysis of the acetyl dimethyl derivative 4. Detailled spectral information is given for the previously unknown benzindenylid-quinone molecule, e.g. the assignment of the 13C NMR signals. 2 is probably formed in a complex reaction from two Juglomycin C units involving a late C—C-bond cleavage.
Notizen: The Crystal Structure of β-CsReO4, the Room-Temperature Modification of Cesium Perrhenate
Authors: Rögner Peter , Range Klaus-Jürgen
Published: March 2015

The crystal structure of β-CsReO4, the roomtemperature modification of cesium perrhenate, was determined from single-crystal X-ray data as orthorhombic, space group P nma, a = 5.7556(9), b = 5.9964(8), c = 14.310(2) Å and Z = 4.

The structure was refined to R = 0.027, Rw = 0.023 for 779 absorption-corrected reflections. It represents an orthorhombic distortion of the tetragonal high-temperature phase α-CsReO4. The structure of β-CsReO4 comprises isolated ReO4 tetrahedra, linked together by Cs ions. The average Re-O distance was found to be 1.714(4) Å.
Notizen: The Crystal Structure of Cesium Fluorotrioxosulfate(VI), CsSO3F
Authors: Rögner Peter , Range Klaus-Jürgen
Published: March 2015

The crystal structure of CsSO3F was determined from single-crystal X-ray data as tetragonal, space group I4,/amd, with a = 5.6317(2), c = 14.1991(9) Å and Z = 4. The structure was refined to R = 0.028,Rw = 0.028 for 403 unique reflections.

In contrast to the earlier literature CsSO3F is not isomorphous with scheelite but with α-CsReO4. The structure contains isolated SO3F tetrahedra which are linked together by twelvefold coordinated Cs ions. The average S–O,F distance is 1.453(3) Å.
Notizen: Über die Darstellung und spektroskopische Charakterisierung von CH3S(Br)F+SbF6
- / On the Preparation and Spectroscopic Characterization of CH3S(Br)F+SbF6-
Authors: Minkwitz Rolf , Bäck Birgit
Published: March 2015

CH3S(H)+SbF6
- reacts in HF as solvent with Br2 to form CH3S(Br)F+SbF6
-. The salt is stable below 195 K and has been characterized by vibrational and 1H and 19F NMR spectroscopy.
Umsetzung von Bis(trimethylgermyl)acetylen und Bis(trimethylstannyl)acetylen mit Diboran(4)-Derivaten / Reaction of Bis(trimethylgermyl)acetylene and Bis(trimethylstannyl)acetylene with Diborane(4)-Derivatives
Authors: Schulz H. , Pritzkow H. , Siebert W.
Published: March 2015

Diboron tetrachloride reacts with bis(trimethylgermyl)acetylene to give 1,1-bis(chlormethylboryl)-2,2-bis(chlordimethylgermyl)ethene (2 b). With 1,2-dichlor-1,2-di-t-butyldiborane(4) the corresponding 1,1-bis(chlor-t-butylboryl)-2,2-bis(trimethylgermyl)ethene (2c) is obtained. Substitution of chlorine atoms in 2b with trimethylsilyldimethylamin leads to the corresponding 1,1-bis(dimethylaminomethylboryl)-2,2-bis(chlordimethylgermyl)acetylene (2 d). The constitution of 2c—2e is derived from NMR and MS data, and confirmed for 2d by an X-ray structure analysis.
Synthese und Kristallstrukturen der 1,3,4-λ5σ4-Diazaphosphole / Syntheses and Crystal Structures of the 1,3,4-λ5σ4-Diazaphospholes
Authors: Stieglitz Gudrun , Neumüller Bernhard , Dehnicke Kurt
Published: March 2015

has been prepared by the reaction of Li(DME)[P(t-Bu)2] with benzonitrile in 1,2-dimethoxyethan solution. The compound forms violet, moisture sensitive crystals, which were characterized by an X-ray structure determination [Space group P21/n, Z = 4, 3282 observed unique reflections, R = 0.082. Lattice dimensions at -40°C: a = 851.0(5), b = 1238.0(3), c = 3029.2(4) pm, β = 90.53(4)°]. The compound forms an ion pair, in which the lithium atom is coordinated by two oxygen atoms of a chelating DME molecule, by an oxygen atom of a nonchelating DME molecule, and by the nitrogen atom of the planar diazaphosphole ring in 1-position. The phenyl groups are nearly coplanar with the diazaphosphole ring.

is the product of the reaction of the lithium complex with methanol. It forms colourless crystals [Space group Ρ21/n, Ζ = 4, 2015 observed unique reflections, R = 0.068. Lattice dimensions at -80°C: a = 1458.3(2), b = 824.8(1), c = 1716.9(2) pm, β = 105.37(9)°]. The molecules have planar 5 H-diazaphosphole rings.
Heterocycle Syntheses through Ternary Condensation of Terephthalaldehyde with Malononitrile and Some Nucleophiles
Authors: Abdel-Latif F. F. , Mashaly M. M. , Mekheimer R. , Abdel-Aleem T. B.
Published: March 2015

The ternary condensation of terphthalaldehyde with malononitrile and some active methylene, and methyl group reagents are reported. Structures and different pathways are described.
Darstellung neuer Monofluorphosphine und einiger ihrer Übergangsmetallkomplexe; Einkristall-Röntgenstrukturanalyse eines Platin(II)-Komplexes / Preparation of New Monofluorophosphines and Some of their Transition Metal Complexes; Single Crystal X-Ray Diffraction Study of a Platinum(II) Complex
Authors: Meyer Thomas G. , Jones Peter G. , Schmutzler Reinhard
Published: March 2015

The reaction of lithiated precursors with PCl2F led to a number of monofluorophosphines, including the known di-tert-butylmonofluorophosphine, 1. Bis(phenylethinyl)monofluorophosphine (2) was accessible only via this route (the classical method of synthesizing 2 by chlorine/fluorine exchange is impossible, because the corresponding chlorophosphine is unknown). Bis(2-methoxyphenyl)fluorophosphine (5) was prepared via the organolithium/PCl2F route. The NMR results for 5 thus prepared were inconsistent with previous reports, implying that the previously reported synthesis of 5 is in error. From 5 a cis-dichloroplatinum(II) complex (6) was synthesized and subjected to a single crystal X-ray structure analysis, confirming the expected planar coordination. From bis(2,3-dimethoxynaphthyl)monofluorophosphine (7) a rhodium(I) (8) and an iron(0)tetracarbonyl complex (9) were prepared. An iron(0)tetracarbonyl complex (11) was synthesized from bis(9-anthryl)monofluorophosphine (10) which was found to be stable to redox disproportionation.
Na8TiAs4, eine neue Zintl-Phase mit idealen isolierten TiAs4-Tetraedern / Na8TiAs4, a New Zintl-Compound with Ideal Isolated TiAs4-Tetrahedra
Authors: Stuhrmann Jürgen , Adam Arnold , Schuster Hans-Uwe
Published: March 2015

The new cubic compound Na8TiAs4, a = 1376.7(1) pm, space group Fd 3 m, is isostructural to Na8SnSb4 [1]. The structure is characterized by ideal isolated TiAs4 tetrahedra. The compound is in agreement with the Zintl concept.
Synthesis and Structure of Di-[µ-acetato(O,O′)-ferrocenylmethyliden-2,4,6-trimethylaniline(N,C)-palladium(II)]
Authors: Blanco Jorge , Gayoso Eduardo , Vila José Manuel , Gayoso Miguel , Maichle-Mössmer Cäcilia , Strähle Joachim
Published: March 2015

Reaction of Na2PdCl4 with N-ferrocenylmethylidene-2,4,6-trimethylaniline yields the dimeric, chloro-bridged Pd(II) complex [Pd{(C5H5)FeC5H3C(H)=N-2,4,6-(CH3)3C6H2}Cl]2. The title complex (1) is obtained by substitution of the chloro-bridges with acetate. 1 crystallizes in the orthorhombic space group Pbca with the lattice parameters a = 1346.4(4), b = 2876.6(2), c = 2472.8(5) pm and Z = 8. In the dimeric complex each Pd2+ cation exhibits a square-planar coordination by the N atom and an ortho-C atom of the cyclopentadienyl ring of the Schiffbase and two oxygen atoms of two different bridging acetato groups.