bluuebunny/crossref_metadata_2025 huggingface dataset:
Zur Kenntnis von Hydridhalogeniden MHX der Seltenen Erden Eu, Yb und Sm (X = Cl, Br, I) / A Study on Hydride Halide Compounds MHX of the Rare Earths Eu,Yb, and Sm (X = Cl,Br,I)
Authors: Beck H. P. , Limmer A.
Published: February 2015

New hydride halide compounds MHX (M = Eu, Yb, Sm; X = Cl, Br, I) of divalent rare earths have been prepared by solid-state reactions. Lattice parameters and X-ray diffraction patterns are presented for these compounds. All compounds are isostructural with tetragonal PbFCl. Refined lattice parameters of alkaline earth hydride halides are given. The crystal chemistry of MHX and MFX is compared and the geometric variations in the structure of these compounds are interpreted on the basis of changes in covalency
Struktur und Schwingungsspektrum des Tetraguanidiniumditellurats, [C(NH2)3]4Te2O6(0H)4 / Structure and Vibrational Spectrum of Guanidiniumditellurate, [C(NH2)3]4Te2O6(0H)4
Authors: Fuchs Joachim , Loederich Reinhard , Pickardt Joachim
Published: February 2015

Guanidiniumditellurate obtained from aqueous solution at room temperature forms triclinic crystals of space group P1̄ with lattice parameters a = 17.486(4) Å, b = 8.459(7) Å, c = 7.134(8) Å; a = 107.42(2)°, β = 83.95(2)° and y = 103.14(2)°. The unit cell contains two crystallographically independent anions with symmetry centers at 0, 0, 0 and 1/2, 0, 1/2. They consist of two octahedral TeO4(OH)2 units which share two common oxygen atoms. The guanidinium ions are connected over an irregular network of bridging hydrogens and terminal oxygen atoms of the anions, in similar manner as ditellurate ions are joined by water molecules in aqueous solutions: the Raman spectrum of the guanidinium salt is nearly identical with the solution spectrum of a ditellurate, but exhibits pronounced differences regarding the spectrum of the solid potassium salt K4Te2O6(OH)2 • 7 H2O
Ein- und zweikernige, anionische Komplexe mit dem Bis(diethoxyphosphinoyl)phosphido-Liganden / One and Two Nuclear Anionic Complexes with the Bis(diethoxyphosphinoyl)phosphido Ligand
Authors: Weber Dieter , Fluck Ekkehard , von Schnering Hans-Georg , Peters Karl
Published: February 2015

The central phosphorus atom of the anion 2 in piperidinium bis(diethoxyphosphinoyl)- phosphide acts as an electron donor towards one or two M(CO)5 groups (M-Mo,W) forming the crystalline coordination compounds 4 and 5. The NMR and IR spectra as well as the X-ray diffraction data are presented
57Fe-Mößbauer-Messungen an μ3-RP-verbrückten heterometallischen Clustern μ3-RP-(C5H5(CO)2Mn)Fe2(CO)6Ln (n = 0,1, 2; L - CO, R3X mit X = P, As, Sb und R = Ph, OPh, OMe) / 57Fe Mößbauer Spectra of //3-RP-Bridged Heterometallic Clusters μ3-RP-(C5H5(CO)2Mn)Fe(CO)6Ln (n = 0, 1, 2; L = CO, R3X with X = P, As, Sb and R = Ph, OPh, OMe)
Authors: Schäfer-Stahl Hartwig , Schneider Josef , Huttner Gottfried
Published: February 2015

Room-temperature Mössbauer spectra are reported for μ3-RP-bridged heterometallic iron clusters of the type μ3-RP-(C5H5(CO)2Mn)Fe2(CO)6Ln. The Mössbauer parameters of these clusters show that the structures are in agreement with the lattice constants of low-spin hetero manganese-iron clusters
Übergangsmetall-Carben-Komplexe, CXXIII [1] Dicarbenoktacarbonyldirhenium-Komplexe / Transition Metal Carbene Complexes, CXXIII [1] Dicarbeneoctacarbonyldirhenium Complexes
Authors: Fischer Ernst Otto , Rustemeyer Paul
Published: February 2015

The reaction of Re2(CO)10 with LiSi(C6H5)3 and subsequent alkylation by (C2H5)3OBF4 yields not only (CO)9Re2C(OC2H5)Si(C6H5)3 but also Re1-ax,Re2-eq-[C(OC2H5)Si(C6H5)3]2(CO)8Re2 (1). The analogous isomeric complexes Re1-ax-[C(OC2H5)C6H4CH3]-Re2-eq-[C(OC2H5)Si(C6H5)3](CO)8Re2 (2) and Re1-ax-[C(OC2H5)Si(C6H5)3]-Re2-eq-[C(OC2H5)C6H4CH3](CO)8Re2 (3) are obtained by treatment of eq- or ax-(CO)9Re2C(OC2H5)Si(C6H5)3 with LiC6H4CH3 and subsequent alkylation by (C2H5)3OBF4. Reaction conditions, and properties and spectroscopic data of the new compounds are reported
A Comparative Study of Metal Shielding in Low Valent Vanadium, Niobium and Manganese Complexes
Authors: Rehder Dieter , Bechthold Hans-Christoph , Keçeci Ahmet , Schmidt Hartwig , Siewing Michael
Published: February 2015

Variations of the metal chemical shifts δ(51V), δ(55Mn) and δ(93Nb) with the paramagnetic deshielding contribution to the overall shielding are discussed in terms of influences imposed by the ligand field splitting, the nephelauxetic effect and the covalency of the metal-to-ligand bond. Complexes under investigation are isoelectronic and/or iso-structural series [M(CO)6-nLn]q (M = V, Nb: q = -1; M = Mn: q = + 1; n = 0-6), η5-C5H5M(CO)4-nLn (M = V, Nb; n = 0-4) and η5-C5H5M(L')2L (M = V, L' = NO; M = Mn, L' = CO). L is a monodentate or l/n oligodentate phosphine. η varies with the point symmetry of the complex, and with ligand parameters of primarily electronic or steric origin. Generally, for weak to medium π-interaction, there is a decrease of shielding with decreasing π-acceptor power of the ligand, increasing ligand bulkiness, increasing ring strains in chelate structures and increasing degree of substitution. For strong π-interaction, the trends may be interconverted. PF3 is shown to be a slightly weaker π-acceptor than CO. Selected results on nuclear-spin spin coupling constants, 13C and 31P shielding are also presented
Compounds of Complex Halo and Pseudohalo Acids of the Group IIB Metals, Part V [1] Preparative and Spectroscopic Studies of the [Hg2I5]-, [Hg2I6]2- and [Hg3I8]2- Ions
Authors: Perlepes S. P. , Zafiropoulos Th. F. , Anagnostopoulos A. K. , Galinos A. G.
Published: February 2015

The preparations of new compounds, containing the complex anions [Hg2l5]-, [Hg2l6]2- and [Hg3I8]2-, are reported.

Distorted iodine-bridged configurations are proposed for the complexes in the solid state, utilising analyses, X-ray powder patterns, molar conductance measurements and spectral (IR, UV) data
Synthese und pharmakologische Eigenschaften von 4.4-Diphenyl-4-sila-piperidinen / Synthesis and Pharmalogical Properties of 4,4-Diphenyl-4-sila-piperidines
Authors: Gerlach Manfred , Jutzi Peter , Stasch Johannes-Peter , Przuntek Horst
Published: February 2015

4,4-Diphenyl-4-sila-piperidines 3 a-d and their hydrochlorides 4 a-d could be synthesized by two different methods starting from diphenyldivinylsilane (Scheme 1). Some properties of these compounds are described. They are the silicon analogues of the well known neuropharmaca 10. Preliminary pharmacological investigations show that the sila-compounds 4a-c have interesting affects concerning to the content of neurotransmitter in the homogenate of rat brains and to the bonding to different receptors
Reaktionen mesoionischer Fünfringheterocyclen mit o-chinoiden Verbindungen, VI [1] Thermische Umlagerung eines [π4+π4]-Cycloaddukts / Reactions of Five-Membered Mesoionic Heterocycles with o-Quinonoid Compounds, VI [1] Thermal Rearrangement of a [π4+π4]-Cycloadduct
Authors: Friedrichsen Willy , Schwarz Ingo , Debaerdemaeker Tony
Published: February 2015

3,5-Di-tert-butyl-o-benzoquinone (1) reacts with 3-methyl-2,4-diphenyl-l,3-oxazolium- 5-olat (2) to give a [π4 + π4] adduct (3). Under thermal conditions compound 3 rearranges to give 5 and 6. The structure of 5 has been clarified by X-ray crystallography
η3-Allyl-Stabilized 'Ate Complexes of Nickel, Palladium and Platinum
Authors: Holle S. , Jolly P. W. , Mynott R. , Salz R.
Published: February 2015

Organolithium compounds react with the bis- (η3-allyl)metal complexes of nickel, palladium and platinum by addition to give ionic 'ate complexes in which one allyl group has been converted into the η1 -allyl form
Synthese eines Doppel-Carbodiphosphorans und seiner Vorstufen / Synthesis of a Double-Carbodiphosphorane and its Precursors
Authors: Schmidbaur Hubert , Costa Thomas
Published: February 2015

The reaction of 1,4-dibromobutane with bis(diphenylphospliino)methane (1) yields two products, one of which is identified as butane-1,4-bis[diphenyl(diphenylphosphinomethyl)-phosphonium bromide] (3 a). Transylidation of this bis-phosphonium salt using two equiv-alents of (CH3)3P = CH2 affords the bis-ylide [CH2CH2P(C6H5)2 = CH-P(C6H5)2]2 (4) in high yields. This conversion can be reversed on treatment of 4 with etheral HCl (to give 3b). Methylation of 4 with CH3I occurs at phosphorus, however, and produces the bis-semiylide salt (5), [CH2CH2P(C6H5)2CHP(C6H5)2CH3]2
2⊕ 2I⊖. Transylidation of 5 (again with (CH3)3P = CH2) leads to the bis-carbodiphosphorane (6), [CH2CH2P(C6H5)2 = C = P(C6H5)2CH3]2. All compounds were characterized by elemental and detailed NMR analyses. The second product of the above quaternisation reaction is a cyclic bis-phosphonium salt (2) with a seven-membered ring structure.
η2-Koordination eines Hydroxylamid(2-)Anions: Die Kristallstruktur von [Mo(NO)(terpy)(CN)(HNO)] 2H2O / η2-Coordination of a Hydroxylamido(2-) Anion: The Crystal Structure of [Mo(NO)(terpy)(CN)(HNO)]2H2O
Authors: Wieghardt Karl , Holzbach Wolfgang , Weiss Johannes
Published: February 2015

The red, diamagnetic complex [Mo(NO)(terpy)(CN)(HNO)] • 2H2O crystallizes in the triclinic space group P1̅(C1
i-No2) with cell constants a = 867.1(3), b = 1008.4(4), c = 1095.6(3) pm, a = 73.64(3)°, β = 83.54(3)°, γ = 83.16(3)°, and Z = 2. The final R value of the single crystal X-ray analysis is 0.063 for 1922 unique reflections. The structure consists of neutral complexes of [Mo(NO)(terpy)(CN)(HNO)]. The geometry about the molybdenum is a distorted pentagonal bipyramid with a linear NO and CN group in the axial positions, a triclentate terpyridine ligand and an O,N-coordinated HNO2- ligand in equatorial positions.
Über Oxostannate(II), IV [1] Zur Kenntnis von Rb2SnO2 und K2SnO2 [2] / On Oxostannates(II), IV Rb2SnO2 and K2SnO2
Authors: Braun Rolf M. , Hoppe Rudolf
Published: February 2015

The new compound Rb2SnO2 was obtained as a light yellow powder by heating mixtures of the binary oxides (RbO0.48 + SnO, Rb: Sn = 2:1) under argon (sealed Ag cylinders, 600 °C, 3d). Subsequent annealing (550 °C, 8d and 500 °C, 17 d) led to light yellow transparent single crystals. Rb2SnO2 is extremely sensitive to moisture and decomposes into black products. It crystallizes orthorhombicly in the space group P212121-D4
2, with a = 5.761, b = 7.493, c= 11.167 Å, Z = 4, drö = 4.43 and dpyk = 4.46 gcm-3 , R= 11.8 and Rw = 12.0%. Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, and the Madelung Part of Lattice Energy, MAPLE, have been calculated. Isotypic K2SnO2 was obtained similarly as a brown powder, a = 5.579, b = 7.246, c = 16.744 Å.
Die Kristallstruktur des 2:1-Adduktes von Antimontribromid mit Biphenyl, 2SbBr3 · C12H10 / The Crystal Structure of the 2 : 1 Adduct of Antimony Tribromide with Biphenyl, 2SbBr3-C12H10
Authors: Lipka Annegret , Mootz Dietrich
Published: February 2015

The crystal structure of 2 SbBr3 · biphenyl consists of pyramidally shaped SbBr3 molecules and planar biphenyl molecules which form a centrosymmetric complex through bonding of the Sb atoms to the phenyl rings. The distance of the Sb atoms to the phenyl ring planes is 323 pm. Taking into account intramolecular bonds Sb-Br at an average of 250.9 pm, an intermolecular Sb···Br contact at 369.5 pm and the π-donor-acceptor inter-action the Sb coordination is distorted ψ-octahedral. The structure is discussed with regard to related compounds.
cis- und trans-Halogeno(2-N.N-dimethylaminophenyl)bis- (triphenylphosphan)platin(II). Synthesen, Struktur und Isomerisierungen / eis- and trans-Halogeno(2-N,N-dimethylaminophenyl)bis(triphenylphosphane)platinum(II). Syntheses, Structure and Isomerizations
Authors: Wiege Manfred , Brune Hans Albert , Klein Heinz-Peter , Thewalt Ulf
Published: February 2015

cis-Chloro(2-N,N-dimethylaminophenyl)bis(triphenylphosphane)platinum(II) and cis-Bromo(2-N,N-dimethylaminophenyl)bis(triphenylphosphane)platinum(II) have been syn-thesized and converted to the corresponding trans-isomers. The crystal and molecular structure of imns-chloro(2-N,N-dimethylaminophenyl)bis(triphenylphosphane)platinum-(II) has been determined by X-ray diffraction. The molecular structure is discussed with respect to possible coordination of the ortho-located N,N-dimethylamino substituent with the central atom.
Protonkatalysierte Wasser-Abspaltung aus 1-Dekalon und 8α-Methyl-1-dekalon in the Gasphase. Verlust der stereochemischen Integrität der cis/traras-Ringverknüpfung bei [MH]+ -Ionen / Proton Catalyzed Water Elimination from 1-Decalon and 8α-Methyl-1-Decalon in the Gas Phase. Loss of the Stereochemical Integrity of the cis/trans Ring Juncture for [MH]+ Ions
Authors: Wrolfschütz Roland , Halim Hermann , Schwarz Helmut
Published: February 2015

Water loss from protonated gaseous 1-decalon and 8α-methyl-1-decalon under the condition of chemical ionisation mass spectrometry proceeds via at least three distinct pathways, all of which commences with a [1.2]-hydrogen or [1.2]-methyl migration, thus giving rise to the formation of the central intermediate 10. H2O loss from 10 proceeds either directly, involving a hydrogen from the position (C-4a) (Scheme 3; pathway 10 →15 →16), or from the rearranged ions 17 and/or 20. The fact that eis-and trans-8α-methyl-1-decalones and their deuterated isotopomers behave essentially identical is explained by loss of the stereochemical integrity of the ring conjunction. The mechanistic features of this unusual process (Scheme 2) have been explored by semi-empirical MINDO/3 calculations for the model system 23 (Scheme 4). The calculations reveal that there are two competing pathways for CH3 migration, one involving a sequence of [1.2]-shifts (23 →24 →25 →26→27), the other -being energetically less favoured -corresponds to a direct [1.3]-methyl migration (Scheme 6; 23 →33 →27), in which the methyl group migrates with retention of configuration. This process is symmetry forbidden. For the corresponding symmetry allowed [1.3]-methyl migration with inversion of configuration of the migrating group no pathway could be detected computationally. Both the experi-mental and theoretical investigations allow one to draw a detailed picture of H2O loss from protonated cyclic ketones in the gas phase. -The syntheses of the labelled substrates are described in detail.
Novel Sublimable Dithioates-Pyridinium and Picolinium Dithiocarboxylates
Authors: Kato Shinzi , Chiba Shinya , Mizuta Masateru , Ishida Masaru
Published: February 2015

Pyridinium Dithiocarboxylates, Picolinium Dithiocarboxylates Pyridinium and picolinium dithiocarboxylates, which can be readily obtained from the corresponding dithio acids and pyridine or picoline, were found to sublimate easily under the conditions of ca. 3 torr at room temperature.
An Improved of α-(Thioaeylthio)methylphenyl-Ketones using Caesium Dithioates and a Convenient Synthesis of 2,4-Disubstituted 1,3-Thiazoles via the Ketones
Authors: Kato Shinzi , Yamamoto Sakae , Ando Kohji , Itoh Katsumi , Mizuta Masateru , Ishida Masaru
Published: February 2015

α-(Thiocylthio)methylphenylketones, 2,4-Disubstituted 1,3-Thiazoles, Caesium Dithioates α-(Thioacylthio)methylphenylketones were found to be obtained in almost quantitative yields from caesium dithioates and a-phenacyl bromide. Refluxing of these ketones with ammonium acetate in gracial acetic acid affords the corresponding 2,4-disubstituted 1,3-thiazoles. While, the similar reaction of α-(thioisobutyrylthio)methylphenylketone gives the dithiafulvene (4).
Zur Chemie des Ingenols, II [1] Ester des Ingenols und des ⊿7.8 -Isoingenols / On the Chemistry of Ingenol, II [1] Esters of Ingenol and ⊿7.8 -Isoingenol
Authors: Sorg Bernd , Hecker Erich
Published: February 2015

Preparation and purification of 3-acylates of ingenol (1a) structurally related to naturally occuring, irritant and cocarcinogenic principles are described. It is shown that 3-acylates partly rearrange to corresponding 5-acylates when they are chromatographecl. From the 3-acylates or from ingenol (1a) a mixed and a symmetric ingenol-3,20-diacylate is synthesized respectively. Ingenol-5,20-acetonide (2a) is rearranged to its ⊿7.8-isomer 3b. Starting with 3b ⊿7.8-isoingenol (3a) and the 3-tetradecanoate of ⊿7.8-isoingenol (3d) are prepared. Most of the ingenol derivatives prepared are tested for their irritant activity on the mouse ear.
The Synthesis of 11-Methoxynauclefine and 11-Methoxyrutaecarpine
Authors: Rahman Atta-ur , Ghazala Maryam
Published: February 2015

Keywords

The synthesis of 11 -methoxynauclefine and 11 -methoxyrutaecarpine is described starting from harmaline.
Zur Reaktion von Fluorcyan: Darstellung von N-Trifluormethyl - S-trifluormethyl-schwefelfluoridimid, CF3-NSF(CF3), und -schwefelchloridimid, CF3-NSCl(CF3) / Reaction of Cyanogen Fluoride : Preparation of N-Trifluoromethyl-S-trifluoromethyl- imidosulfurfluoride, CF3-NSF(CF3) and -imidosulfurchloride, CF3-NSCl(CF3)
Authors: Leidinger Walter , Sundermeyer Wolfgang
Published: February 2015

N-Trifluoromethyl-S-trifluoromethylimidosulfurfluoride and chloride CF3NSX(CF3) (X = F, Cl) were obtained from cyanogen fluoride and trifluoromethylsulfurtrifluoride and subsequent halogen exchange, respectively.
Organoaluminum Radical Complexes from the Single Electron Transfer Reaction of Diisobutylaluminum Hydride with N-Heterocycles
Authors: Kaim Wolfgang
Published: February 2015

Diisobutylaluminum hydride iBu2AlH reacts with N-heterocycles L (L = pyrazine, 2,2'-bipyridine, 4,4'-bipyridine) via single electron transfer to yield 1:1 radical complexes [L(AliBU2)·].
Kristallstrukturen und Schwingungsspektren des Heteropolysulfats [N(CH3)4]6S2V2W16O62 und des Vanadatowolframats Na[N(CH3)4]2VW5O19 · H2O / Crystal Structures and Vibrational Spectra of the Heteropolysulfate [N(CH3)4]6S2V2W16O62 and the Vanadatotungstate Na[N(CH3)4]2VW5O19 · H2O
Authors: Botar Alexandru , Fuchs Joachim
Published: February 2015

X-ray analysis of [N(CH3)4]6S2V2W16O62 furnishes evidence for the existence of a discrete heteropolysulfate ion. The compound crystallizes monoclinic, space group P21/C with lattice parameters a = 13.361(5) Å, b = 25.378(1) Å, c = 28.847(5) and β = 91.37(3)°. Its anion has the configuration (Dawson structure) first observed in K6P2W18O62 · 14 H2O. [N(CH3)4]2NaVW5O19 · H2O, formed as a side product in the preparation of the hetero-polysulfate, crystallizes in the orthorhombic space group Pmnm with lattice constants a = 12.810(3) Å, b = 10.842 Å and c = 9.703(4) Å. Its anion belongs to the known hexa-metallate type M6O19
z− . The sodium ion is pentacoordinate (trigonal bipyramidal). The water of crystallization belonging to its coordination sphere exhibits the extremely short Na-O distance of 2.19 Å. The Na+ ··· H2O grouping appears to cause an IR as well as Raman active vibration band at 1290 cm-1 .
Darstellung von Diphenylbismutcarboxylaten / Preparation of Diphenylbismuth Carboxylates
Authors: Huber Friedo , Bock Sigrid
Published: February 2015

Diphenylbismuth carboxylates Ph2BiX (X = OAc = CH3COO, C2H5COO, C3H7COO, Me2CHCOO, Me3CCOO, CH3COCH2CH2COO, PhCOO; Me = CH3; Ph = C6H5) have been prepared from Ph2BiCl and NaX or from Ph2BiOC2H5 and HX in anhydrous ethanol. PhoBiOAc and a compound of approximate composition PhBi(OAc)2 have been obtained in small yields from acidolysis of Ph3Bi with HOAc (molar ratio 1:1 and 1:3, resp.) in acetone. A polymeric structure with bridging bidentate carboxylate groups is proposed for Ph2BiX compounds.
Darstellung und Kristallstruktur von KNaO und RbNaO / Preparation and Crystal Structure of KNaO and RbNaO
Authors: Sabrowsky Horst , Schröer Ulrich
Published: February 2015

Potassium Sodium Oxide, Rubidium Sodium Oxide The compounds KNaO and RbNaO have been prepared and their structures determined by powder and single crystal data. Both compounds show the anti-PbFCl crystal structure type with two molecular units. KNaO: a = 400.2(1) pm, c = 621.4(2) pm, c/a= 1.553; RbNaO: a = 409.3(9) pm, c = 653.1(9) pm, c/a = 1.595.
Synthesen von Adenin und Guanin aus Ammoniumcyanid und Cyansäure in Zeolith X / Synthesis of Adenine and Guanine from Ammonium Cyanide and Cyanic Acid in Zeolithe X
Authors: Seel Fritz , Blon Martin von , Dessauer Andreas
Published: February 2015

Adenine (1) is formed in substantial amounts (about 1% yield) by heating ammonium cyanide absorbed in zeolithe X for several days at 120 °C. If both, ammonium cyanide and cyanic acid have been absorbed, 1 and guanine (2) are synthesized under the same conditions. These experiments provide the first demonstration of the possibility of a spontaneous synthesis of these essential constituents of nucleic acids and of important coenzymes in a silicate.
The Crystal Structure of Carbonyl Gold(I) Chloride, (OC)AuCl
Authors: Jones Peter G.
Published: February 2015

The crystal structure of (OC)AuCl has been determined and refined to R 0.037 (space group Cmcm, a = 407.1(1), b = 1042.2(4), c = 532.1(3) pm, Z =4). The structure consists of discrete, exactly linear molecules; all atoms lie on the special positions 0, y, 1/4. The bond lengths involving the light atoms are affected by libration. The shortest Au ··· Au contacts between molecules are 338 pm.
On the Structure of the Claasz's Sulfurylindoxyl
Authors: Somogyi László
Published: February 2015

On chemical, IR and 1H NMR spectroscopic evidences the structure of the so-called sulfurylindoxyl was found to be 2-aminophenyl methyl sulfone (4) and not the benzo-thiazoline-1,1-dioxide (7) claimed by Claasz [1]. Contrary to data in the literature [2] the title compound gives only one sort of monoacetyl derivatives: 2-acetamidophenyl methyl sulfone (10). An unambiguous synthesis of 3-acetylbenzothiazoline-1,1-dioxide (8) is presented.
Übergangsmetall-substituierte Phosphane, Arsane und Stibane, XXX Redoxreaktionen zwischen Triorganodibromphosphoranen oder -arsoranen und Ubergangsmetall -Anionen / Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XXX Redox Reactions between Triorganodibromophosphoranes or -arsoranes and Transition Metal Anions
Authors: Meyer Angelika , Hartl Anna , Malisch Wolfgang
Published: February 2015

The reaction of the sodium carbonyl metalate Na[W(CO)3Cp] with the phosphorane (Me3SiCH2)3PBr2 results in the formation of (Me3SiCH2)3PandCp(CO)3WBr or [Cp(CO)3W]2, respectively, depending on the solvent used. The redox reactions between Na[Mo(CO)3Cp] and the arsenic analogue (RCH2)3AsBr2 (R = Ph, Me3Si) yield the products Cp(CO)sMoBr and (RCH2)3As. A mechanism involving radicals is discussed. At elevated temperatures the products react further to give the square pyramidal complexes cis-Cp(CO)2[As(CH2R)3]MBr (1, 2a, b) with loss of CO. In an analogous manner Cp(CO)3MBr (M = Mo, W) and (RCH2)3E (E = As, Sb) afford compounds cis-Cp(CO)2[E(CH2R)3]MBr (2c, 3). The dynamic behaviour of the chiral complexes 1, 2a, b, was investigated by 1H NMR spectroscopy.
2.5-Dihydro-und Tetrahydro-2.2-dimethyl-3-thiophenaldehyd / 2,5-Dihydro-and Tetrahydro-2,2-dimethjd-3-thiophenealdehyde
Authors: Sucrow Wolfgang , Müller Hans-Walter
Published: February 2015

The preparation of the title aldehydes 1 and 6 a, the corresponding alcohols 2 a and 6 b and some other derivatives is described.
Preparation and Structures of Ternary Copper(II) Complexes of ADP and ATP Models for Enzyme-Metal Ion-Nucleoside Polyphosphate Complexes
Authors: Sheldrick William S.
Published: February 2015

The stable ternary copper(II) complexes of ATP and ADP, [Cu(H2ATP)(phen)]2 · 7 H2O (2) and [Cu4(HADP)2(bipy)4(H2O)2(NO3)2] · 2 NO3 (3), have been isolated from aqueous solution at respective pH values of 2.8 and 4.0. Their structures have been established by single crystal X-ray diffraction. Tridentate coordination of each of the Cu atoms by ono α-, one β- and one γ-phosphate O atom of one ATP molecule is observed in 2. The binding Oα atoms occupy axial positions in a distorted octahedral geometry at Cu and the Cu- Oα interactions are weak. The other axial position is occupied by a γ-phosphate O atom of the second ATP molecule, leading to a dimeric structure. The basic structure of 3 is similar with, in this case, bidentate coordination of each of the central Cu atoms by one α- and one β-phosphate O atom of ono ADP molecule. In this case, however, the third terminal β-phosphate O atoms each bind a further Cu atom. All four Cu atoms in 3 display square pyramidal coordination. The structures of 2 and 3 are stabilised by intramolecular stacking of adenine and phenanthroline/bipyridyl systems. The significance of these structures as models for enzyme-metal ion-nucleoside polyphosphate complexes is discussed.
Antiovulatory Potency and Conformation of an Antagonist of the Luteinizing Hormone-Releasing Hormone Having Six D-Amino Acids
Authors: Folkers Karl , Bowers Cyril Y. , Momany Frank , Friebel Klaus J. , Kubiak Teresa , Mahera Joseph
Published: February 2015

[N-Ac-Thr 1 ,D-Phe 2,D-Trp 3,6]-LHRH was the model antagonist of LHRH, which was the basis for tho design, synthesis and bioassay of seven peptides having four, five and six D-amino acids, which resulted from three single, three double, and one triple introductions of D-amino acids in positions 4, 5 and 8 of the model. Only the analog with six D-amino acids, [N-Ac-Thr 1,D-Phe 2 ,D-Trp 3,D-Ser 4, D-Tyr 5 ,D-Trp 6 ,D-Arg 8]-LHRH, had antiovulatory activity which was higher than that of the model antagonist, i.e., 70% antiovulatory activity at 25 μg/rat compared with 50% activity at 50 μg/rat, respectively. Empirical energy calculations gave a conformational structure for [N-Ac-Thr 1,D-Phe 2,D-Trp 3, D-Ser 4,D-Tyr 5,D-Arg 6,D-Arg 8]-LHRH which is similar to that calculated for previous potent antagonists. These results are a basis of new designs of antagonists having D-sub-stituents in up to ten positions toward effective inhibitors of ovulation by the parenteral and oral routes of administration.
2-Phenylthiazol-Derivate aus Pseudomonas cepacia / 2-Phenylthiazole Derivatives from Pseudomonas cepacia
Authors: Bukovits G. J. , Mohr N. , Budzikiewicz H.
Published: February 2015

From the culture medium of Pseudomonas cepacia 2-(o-hydroxyphenyl)-thiazol and its 4-carbaldehyd and 4-carboxylic acid derivatives (aeruginoic acid) could be isolated. Their structures were elucidated and confirmed by synthesis.
Umwandlung von 5H-Dibenz[c.e]azepinen in Phenanthridine über cyclische N-Diazonium-Ionen / Conversion of 5H-Dibenzo[c,e]azepines into Phenanthridines via Cyclic N-Diazonium Ions
Authors: Kreher Richard , Bergmann Udo
Published: February 2015

The reaction of 6-amino-6,7-dihydro-5H-dibenzo[c,e]azepine, bearing a terminal blocking group, with trifluoracetylnitrite presumably proceeds via cyclic 7-membered N-diazonium ions and mainly leads to the formation of phenanthridine by migration of the aryl group. 5H-Dibenzo[c,e]azepine can be isolated as the minor product and seems to be the result of a hydrogen shift. N ,N′-Azo-6,7-dihydro-5H-dibenzo[c,e]azepine dis-plays an analogous behaviour.
Funktionelle Derivate von Phenoxyplienoxypropionsäuren und ihre herbizide Wirksamkeit / Derivatives of Phenoxyphenoxypropionic Acids and their Herbicidal Activity
Authors: Handte Reinhard , Koch Manfred , Bieringer Hermann , Hörlein Gerhard
Published: February 2015

Derivates of phenoxyphenoxypropionic Acids are herbicids with high activity. Methods to synthesis these compounds are reviewed. Relationship between structure and herbicidal activity are discussed.
Notizen: Die Kristallstruktur von Hexametliylentetrammoniumtrichloromercurat (II), [C6H13N4] [HgCl3}] / The Crystal Structure of Hexamethylenetetrammoniumtrichloromercurate( II), [C6H12N4][HgCl3]
Authors: Pickardt Joachim , Schendler Thomas
Published: February 2015

By the react ion of mercuric chloride and hexamethylenetetramine in aqueous solution crystals of the title compound could be obtained. The compound contains planar trichloromercurate (II) anions; in the crystal they form infinite chains, interlinked by chloride bridges.
Crystal Structure of Tetrakis(triphenylstibine)gold(I) Bis (pentafluorophenyl) aurate ( I )
Authors: Jones Peter G.
Published: February 2015

The crystal structure of the title compound has been determined (P3c 1, a = 2161.5(3), c = 2859.8(4) pm, Z = 6; Rw = 0.07 for 2217 observed reflections). There are three independent (Ph3Sb)4Au+ cations, each with one Au-Sb bond directed along a crystallo-graphic threefold axis. Deviations from ideal tetrahedral coordination are small (max. 8 pm, 1°).
Darstellung und Kristallstruktur von Gold(III)selenitchlorid, Au(SeO3)Cl/Preparation and Crystal Structure of Gold(III) Selenite Chloride, Au(SeO3)Cl
Authors: Jones Peter G. , Kraushaar Martin , Schwarzmann Einhard , Sheldrick George M.
Published: February 2015

Au(SeO3)Cl was prepared in a sealed-tube synthesis from Au2Se4O11, selenic acid and perchloric acid. The crystal structure was determined (P1̄, a = 418.5(1), b = 975.6(4), c = 1060.8(5) pm, α = 80.57(2), β = 88.85(2), γ = 87.66(2)°, Z = 4, R = 0.06 for 2273 observed reflections). There are three independent gold atoms in the structure, belonging to AuO4, AuO2Cl2 and AuO3Cl units respectively. The oxygen atoms bridge Au and Se, leading to a polymeric layer structure.
Ylid-Komplexe von Alkali- und Erdalkalimetallen, VI [1] Neutrale und anionische Ferrocenylmethylide und Fluorenylide/Ylide Complexes of Alkali and Earth Alkaline Metals, VI [1] Neutral and Anionic Ferrocenylmethylides and Fluorenylides
Authors: Schmidbaur Hubert , Deschler Ulrich , Seyferth Dietmar
Published: February 2015

Coordination properties of phosphorus ylides towards electropositive metals are greatly improved in systems, where the carbanionic charge can be delocalized into the aromatic rings of substituents, as illustrated in the title compounds. The ferrocenyl-substituted ylide 2, synthesized from bis(diphenylphosphino)methane and (ferrocenyl)trimethyl-ammonium iodide via the phosphonium salt intermediate 1, is thus easily converted into the alkali complexes 3 a, b on treatment with NaNH2 or KH in tetrahydrofuran, respectively. The intensely coloured products are soluble in a number of organic solvents. NMR spectra of these solutions provide evidence for an interaction between alkali cations and the ferrocenyl rings. - From (C6H5)2CH2P(C6H5)2 and ferrocenylmethyl chloride a di-quaternary salt 4 is obtained, which yields a double-ylide mixture 5 a, b on treatment with base. Hydrolysis of this product affords the ylidic phosphine oxide 6. - The reaction of the ylides 7 and 9 (described previously) with NaNH2, KH or barium metal (in liquid ammonia) leads to the (earth) alkali complexes 8a-c and 10a, b, respectively. With the exception of 8c, but similar to 3a, these materials contain tetrahydrofuran solvate molecules. The 23Na NMR spectrum of 8a and the pronounced quadrupole broadening of the P(III) signals by the alkali cations in the 31P NMR spectra of 8 a, b allow structural suggestions for the solution state as proposed in the formulae. Further treatment of 10b with KH yields a potassium complex 11, characterized, i.a., via a corresponding diquaternary salt 12.
Kohlensäureesterphosphide – Synthese und Cyclisierungsreaktionen/Carbonic Ester Phosphides – Synthesis and Cyclization Reactions
Authors: Thamm Rüdiger , Fluck Ekkehard
Published: February 2015

Carbonic ester phosphides, RPHCOORʹ and RP(COORʹ)2, have been prepared by the reaction of ClCOORʹ with primary phosphines RPH2 in the presence of K2CO3. Some compounds of RPHCOORʹ series are transformed into P-heterocycles through addition of the P-H group to the C = C doublebond systems. The 31P NMR data, IR and mass spectra of the novel compounds are presented and discussed.
Isopoly- und Heteropoly-Thioanionen. Kristall- und Molekülstrukturen von (PPh4)2[(WS4)WS(WS4)],CS2[(WS4)WO(WS4)H2O]·2H2O und (AsPh4)2[(WS4)Ni(WS4)]/Isopoly- and Heteropoly-Thioanions. Crystal and Molecular Structures of (PPh4)2[(WS4)WS(WS4)], Cs2[(WS4)WO(WS4)H2O] · 2 H2O and (AsPh4)2[(WS4)Ni(WS4)]
Authors: Müller Achim , Bögge Hartmut , Krickemeyer Erich , Henkel Gerald , Krebs Bernt
Published: February 2015

The crystal and molecular structures of (PPh4)2[(WS4)WS(WS4)] (1a) and CS2[(WS4)WO(WS4)H2O] · 2 H2O (2a), which contain the first reported isopoly-thioanion of a transition metal have been determined:

1a: (P1̅, a = 913.0(1), b = 1060.1(2), c = 1333.9(2) pm, α = 87.11(1), β = 85.18(1), γ = 83.07(1)°, V = 1277.6 · 106 pm3, Z = 1);

2a: (P21/n, a = 671.6(2), b = 2018.5(4), c = 714.4(2) pm, β = 101.42(2)°, V = 949,3 · 106 pm3, Z = 2)

and compared with that of the trimetallic heteropoly-thioanion of

(AsPh4)2[(WS4)Ni(WS4)] (3a).

3a: (P1̄, a = 1255.2(3), b = 1277.1(3), c = 939.0(2) pm, α = 113.19(2), β = 96.28(2), γ = 108.72(2)°, V = 1261.5 · 106 pm3, Z = 1).

Though there are delocalized orbitals in the isopoly-thioanions they can be regarded as coordination compounds of WIVX2+ containing two WVIS4
2- ligands.
Borkomplexe mit Dicarbonsäuren: Bis(oxalato)borate und Bis(malonato)borate/Boron Complexes with Dicarboxylic Acids: Bis(oxalato)borates and Bis(malonato)borates
Authors: Bessler Eberhard , Weidlein Johann
Published: February 2015

Several bis(oxalato)borates and bis(malonato)borates have been prepared in heterogeneous reaction from boric acid, dicarboxylic acid and dicarboxylic salt by refluxing in benzene under continuous separation of water. The compounds were characterized by their IR and 11B NMR spectra. The vibrational spectra of the bis(oxalato)borate are discussed in detail.
IR-Spektren von Platin(II)-Komplexen mit Glycin, Glycin-und Glycylglycinethylester [1]/IR-Spectra of Platinum(ll) Complexes with Glycine, Glycine Ethyl Ester and Glycylglycine Ethyl Ester [1]
Authors: Kharitonov Jurij Ja. , Bissinger Herbert , Ambach Eberhard , Beck Wolfgang
Published: February 2015

The infrared spectra (200-4000 cm-1) of trans- and cis-Pt(NX2CH2COO)2 (X = H, D), trans- and cis-PtCl2(NH2CH2COOH)2, trans-PtCl2(NH2CH2CO2Et)2, cis-PtCl2(NX2CH2CO2Et)2, cis-PtCl2(NX2CH2NXCH2CO2Et)2 (X = H, D) and cis-PtY2(NH2CH2NHCH2CO2Et)2 (Y = Br, I) including 15N derivatives have been studied. There is no appreciable change of vibrational frequencies for corresponding cis- and trans- complexes which could be attributed to the trans-influence of different ligands. Due to lower symmetry most of the absorptions of the cis-complexes are split into doublets compared with the trans-compounds.
Metallkomplexe funktioneller Isoeyanide, VI [1] Tosylmethyl-, Benzyl- und Benzhydrylisocyanid-Metallverbindungen und ihre Reaktionen mit Nucleophilen und 1.3-Dipolarophilen/Metal Complexes of Functional Isocyanides, VI [1] Tosylmethyl-, Benzyl- and Benzhydrylisocyanide Metal Complexes and Their Reactions with Nucleophiles and 1,3-Dipolarophiles
Authors: Fehlhammer Wolf Peter , Bartel Klaus , Völkl Alfons , Achatz Dagobert
Published: February 2015

Metal complexes of the type M(CO)5L (M = Cr, W), MX2L2 (M = Pd, Pt; X = Cl, Br, I), PtCl2(L)PPh3, and [Pt(Cl)(L)(PPh3)2]BF4 have been prepared with

L = CNCH2SO2C6H4-pCH3, CNCH2Ph, and CNCHPh2, and reacted with a variety of nucleophiles (NH2CH2CO2CH3, CH(CN)2-, CH(CN)CO2CH3-, OH-) and 1,3-dipolarophiles (CF3CN, CH3O2CC ≡CCO2CH3, CH2 = CHCN, RNCO (R = CH3, Ph), RCHO (R = i-C3H7, Ph, C6H4-oOH)) to give carbene, α-aminovinyl, and carboxamido complexes, and C2-metallated heterocycles (imidazoles, pyrroles, oxazolos, oxazolines), respectively. Ready dealkylation occurs of benzhydryl isoeyanide in [Pt(Cl)(CNCHPh2)(PPh3)2]BF4.
Two Dimensional 1H–1H and 13C–1H-Correlation NMR: The Analysis of η3-Allylnickel Complexes
Authors: Benn Reinhard
Published: February 2015

The 1H and 13C NMR spectra of various alkylsubstituted η3-allyl-η5-cyclopentadienyl-nickel complexes were analysed with the help of two dimensional correlation (1H-1H and 1H-13C) NMR. The use of two dimensional NMR techniques for the routine analysis of complicated NMR spectra is demonstrated.
Die photochemische Reaktion von Decacarbonyl-dirhenium mit 1.3-Butadien/The Photochemical Reaction of Decacarbonyl-dirhenium with 1,3-Butadiene
Authors: Franzreb Karl-Heinz , Kreiter Cornelius G.
Published: February 2015

The photochemical reaction of decacarbonyl-dirhenium(0) (1) with 1,3-butadiene yields a mixture of six complexes, which were isolated by HPL-chromatography and characterized by spectroscopic means. As minor products the allylic complexes E and Z tetracarbonyl-η3-1-buten-3-yl-rhenium(I) (2, 3) and RR, SS and SR ≡ RS Octaearbonyl-μ-[1-3:6-8-η-(1,6-octadiene-3,8-diyl)]-dirhenium(I) (7, 8) are obtained. Reaction temperatures of 240 K favour the formation of the novel μ-hydrido-octacarbonyl-μ-[1-2-η-1-δ-(1,3-butadien-1-yl)]-dirhenium(I) (4). At lower temperatures (188 K) octacarbonyl-η-s-cis-1,3-butadienedirhenium(0) (5) results in comparable amounts. 4 rearranges in solution to octacarbonyl-μ-η-trans-1,3-butadiene-dirhenium(0) (6).
Characterisation of a Binary Transition Metal Complex of a 3ʹ,5ʹ-Cyclic Nucleotide [1]. Preparation and Structure of a Nickel(II) Complex of Guanosine 3ʹ,5ʹ-Cyclic Monophosphate
Authors: Sheldrick W. S.
Published: February 2015

[Ni(3ʹ,5ʹ-cGMP)(H2O)5][3ʹ,5ʹ-cGMP] · 5H2O (1) was isolated from an aqueous solution of Ni(NO3)2 and guanosine 3ʹ,5ʹ-cyclic monophosphate at a pH of 6.5. 1 is orthorhombic P212121 with a = 19.020(4), 6 = 7.718(1), c = 12.316(2) Å, Z = 2, Dc = 1.70 g·cm-3. The structure was refined to R = 0.085 and Rw = 0.077 for 1364 independent reflections. The structure of 1 is disordered. The nickel atom has a site occupation factor of 0.5 with the 3ʹ,5ʹ-cGMP moieties of both cation and anion disordered over the same fourfold general positions. Direct metal binding of the purine N(7) is observed with the octahedral co-ordination of the nickel atom being completed by 5 water oxygens, one of which forms an intramolecular O-H···O hydrogen bond to the guanine O(6). The purine base adopts the syn conformation relative to the ribose ring with xCN = -93.3(8)°. The nucleotide bases are stacked in columns along the b screw dyad axes. Parallel to these columns are cavities which are filled by the water molecules and the complexed nickel cations.
Synthesis and Bioassay of Antagonists of the Luteinizing Hormone Releasing Hormone Having the Azagly10 Moiety
Authors: Folkers Karl , Bowers Cyril Y. , Lutz Wilson B. , Friebel Klaus , Kubiak Teresa , Schircks Bernhard , Rampold Georg
Published: February 2015

Seven new analogs of the luteinizing hormone releasing hormone (LHRH), having an Azagly10 moiety, and three corresponding Gly10 -analogs were synthesized for bioassay and comparison of inhibitory potencies. This study was toward a possible advantage of the Azagly10 moiety to minimize C-terminal degradation, in vivo. Of the three procedures which were studied to achieve Azagly10-peptides, the reaction of cyanate ion with hydrazides was the most favorable. Variations of substitution in position 1 were also studied. The data from the antiovulatory assay showed that an Azagly10 moiety may not depress activity, and may allow equal or even higher activity than the Gly10 moiety, depending on the analog. [N-Ac-D-Thr1 , D-p-Cl-Phe2 , D-Trp3,6, Azagly10]-LHRH was more inhibitory than the corresponding Gly10-analog. Based on pairs of analogs, the following relationships appeared: (1) N-Ac-D-Thr1 was more effective than

N-Ac-p-Cl-Phe1 ; (2) The L-configuration of Ala as N-Ac-Ala1- was more effective than the D-; (3) N-Ac-Ala1 appeared more effective than the N-Ac-D-Thr1 ; (4) D-Trp6 appeared more effective than D-Phe6. In an ultimate clinical use of an antagonist of LHRH to block ovulation, the Azagly10 moiety may be advantageous for limitation of enzymatic degradation.
Stoffwechselprodukte von Mikroorganismen, XXVII[1] Cyclopaldsäure und 3-O-Methyl-cyclopolsäure, zwei antibiotisch wirksame Substanzen aus Aspergillus duricaulis/Investigations on Metabolites of Microorganisms, XXVII [1] Cyelopaldic Acid and 3-O-Methyl Cyclopolic Acid, Two Antibiotically Active Substances from Aspergillus duricaulis
Authors: Achenbach Hans , Mühlenfeld Andreas , Weber Benno , Kohl Werner , Brillinger Gert-Ulf
Published: February 2015

3,5-Dihydroxy-4-formyl-7-methoxy-6-methyl-1(3H)-isobenzofuranone [=cyclopaldic acid] (1) and 5-hydroxy-4-hydroxymethyl-3,7-dimethoxy-6-methyl-1(3H)-isobenzofura-none [= 3-O-methyl cyclopolic acid] (2) were isolated from Aspergillus duricaulis-, those compounds were found to be antibiotically active.
Notizen: S4N4 und seine Derivate: Die Struktur von TaCl5 · S4N4/S4N4 and its Derivatives: Structure of TaCl5 · S4N4
Authors: Tliewalt Ulf , Albrecht Gertrud
Published: February 2015

An X-ray structure determination of TaCl5 · S4N4 shows that the S4N4 group is bonded via one of its nitrogen atoms to the Ta atom thus completing the coordination octahedron around the tantalum center.
Reaktionen von Diphenylsulfilimin Ph2SNH mit Carbonylmetallkomplexen/ Reactions of Diphenylsulfilimine Ph2SNH with Carbonyl Metal Complexes
Authors: Urban Günter , Beck Wolfgang
Published: February 2015

The reaction of the carbonyl metal hydrides (π - C5H5)M (CO)3H(M = Mo, W) with Ph2S = XH gives the ainine-isoeyanato compounds (π - C5H5)(CO)2M(NH3)NCO. N-Carbaxnoyl-B,S-diphenylsulfilimine Ph2S N-C(O) NH2 has boon isolated from the reaction of the hexacarbonyls M(CO)6(M=Cr,Mo) with Ph2S = XH. The spectroscopic data (IR, 1H, 13C NMR, MS) are reported and the formation of the products is discussed.
Synthese von Tetraorganodistibanen und oxidative Spaltung zu Bis(diorganoantimon)oxiden und -Sulfiden/ Synthesis of Tetraorganodistibanes and Oxidative Cleavage to Bis(diorganoantimony) Oxides and Sulfides
Authors: Breunig Hans Joachim , Jawad Hussain
Published: February 2015

The tetraorganodistibanes Pr4Sb2 and Ph4Sb2 were prepared by dehalogenation of the corresponding dioganoantimony bromides with magnesium in tetrahydrofuran. Mass spectra show that the distibanes Me4Sb2, Et4Sb2 and i-Pr4Sb2 react with air to yield the compounds of the formula R4Sb2O (R = Me, Et, i-Pr), which are assumed to be bis- (diorganoantimony)oxides. The species (Me2Sb)2O is also formed by hydrolysis of Me2SbBr. Ir and 1H NMR data of this oxide confirm the proposed structure. The distibanes R4Sb2 (R = Me, Et, Pr, Ph) react quantitatively with sulfur to yield the corresponding bis- (diorganoantimony)sulfides (R2Sb)2, as derived from ms, NMR and IH data. Ms data of the distibanes R4Sb2 (R = Me, Et, i-Pr, Bu, Ph) are reported and discussed.
Thermische und Photo-induzierte Substitutionsreaktionen an der Eisen-ethyl-Verbindung CpFe(CO)2Et. Die Molekülstruktur von CpFe(PMe3)2COEt (Cp =η5-C5H5)/ Thermal and Photo-Induced Substitution Reactions of the Iron Ethyl Compound CpFe(CO)2Et. The Molecular Structure of CpFe(PMe3)2COEt (Cp = η5-C5H5)
Authors: Alt H. G. , Eichner M. E. , Jansen B. M. , Thewalt U.
Published: February 2015

The photo-induced reaction of CpFe(CO)2Et (1) with either trimethylphosphane or trimethylphosphite (L) in solution results in formation of the substitution products CpFe(CO)(L)Et (3), CpFe(L)2Et (5), and the hydrido complexes CpFe(CO)(L)H (4), and CpFe(L)2H (0). In contrast, the thermal reaction of 1 with L yields the adduct CpFe(CO)(L)COEt (7) and the dimeric compound Cp2Fe2(CO)3L. Under photochemical conditions, the terminal carbonyl ligand in 7 can be replaced by L to give the derivative CpFe(L)2COEt (8).

According to a crystal structure determination of CpFe(PMO3)2COEt, the complex possesses a η1 -bonded propionyl ligand. The IR and NMR data, however, are indicative for a η2 -bonded propionyl ligand.
Raman-Matrixspektrum von As4/ Raman Matrix Spectrum of As4
Authors: Manzel Klaus , Schulze Wilfried , Wölfel Volker , Minkwitz Rolf
Published: February 2015

The laser Raman spectrum of matrix-isolated As4-tetrahodra is reported. The frequencies are different to former data obtained by gas-phase measurements.
Neues über Fluoride A[CoF4] mit A = Li-Cs sowie über CsFeF4/ News on Fluorides A[CoF4] with A = Li-Cs and on CsFeF4
Authors: Fleischer Thomas , Hoppe Rudolf
Published: February 2015

By fluorination of CsFeBr4 · 2 H2O we obtained a new modification of CsFeF4 (a = 12,491(1), c = 13,272(1) A, Z - 20), which according to powder data crystallizes tetragonally in the structure type of β-RbAlF4, space group I4̄c2. The same structure type is adapted by CsCoF4 (a 12,478(1), c = 12,971(1) Å, Z = 20); in contrast RbCoF4 has similar lattice constants (a = 12,222(1), c = 12,356(2) Å, Z = 20), but another unknown structure; KCoF4 (a = 7,520(1), b = 7,584(1), c = 5,792(1) Å, Z = 4) crystallizes orthorhombic by isotypic to RbFeF4, and NaCoF4 (a - 4,965(1), b = 5,51(5(1), c = 10,800(2) A, Z = 4) is isotypic to NaTiF4. The first compound LiMIIIF4 (MIII = 3dmetals) is LiCoF4, which probably crystallizes monoclinicly (a = 5,540(3), 6 = 4,665(1), c = 5,447(3) Å, = 114,25(5)°, Z = 2). The colour of these cobaltates(III) is violet.
Hydroxo Verbindungen, 11. Zinn(II)-Ethylenglykolat, SnC2H4O2, ein polymerer Chelatkomplex mit 2-fach funktionellem Sauerstoff/ Hydroxy Compounds, 11. Tin(II) Ethylen Glycolate, SnC2H4O2, a Polymerie Chelate Complex with Bi-Functional Oxygen
Authors: Nesper Reinhard , Schnering Hans Georg von
Published: February 2015

Tin(II) ethylene glycolate is prepared from freshly precipitated “tin(II)-hydroxide” on heating in ethylene glycol under reflux. The colourless single crystals, slightly distorted cubes, exhibit rhombohedral symmetry (R3̄-C3i
2, ah = 1547.7 pm, cn= 871.6 pm, Z = 18). The structure is a 3-dimensional networks of linked tin(II) ethylene glycol chelates.
Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XXVI. Nickelaphosphacycloalkane unterschiedlicher Ringgröße - Kristallstruktur von[(h5-C5H5)NiP(C6H5)2CH2]2/ Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, XXVI. Xickelaphosphacycloalkanes with Different Ring Sizes - Crystal Structure of [(h5-C5H5)NiP(C6H5)2CH2]2
Authors: Lindner Ekkehard , Bouachir Faouzi , Hiller Wolfgang
Published: February 2015

Substitution of CO in LNi(I)CO (1) (L = h5-C5H5) by the co-chloro-l-(diphenylphosphino) alkanes Cl-[CH2]n-PR2 (2a-d) [R = C6H5; n = 1(a), 2(b), 3(c), 4(d)] leads to the formation of the intermediates for cyclisation LNi(I)PR2-[CH2]nCl (3a-d). When 3a is treated with sodium amalgam, the dimeric phosphino methanide complex [LNiPR2CH2]2 (4′a) is formed. On the basis of an X-ray crystallographic investigation 4'a has a boat conformation and crystallizes monoclinicly in the space group P21/c with Z = 2. The monomeric species

(4a) could not be observed. Five- and six-membered I 1 nickelacycloalkanes of the type

(4c, d) are obtained by reductive cycloelimination of 3c, d. Because of ring strain the nickelaphosphacyclobutane 4b is not accessible under the necessary cyclisation conditions. Into the Ni-C a bond of 4c, d SO2 can be inserted to give the cyclic sulfinato complexes

(5c, d).
Determination of the Rate Constants of the Reactions CO2+ OH– → HCO3— and Barbituric Acid → Barbiturate Anion +H+ Using the Pulse Radiolysis Technique
Authors: Schuchmann Man Nien , Sonntag Clemens von
Published: February 2015

The kinetics of the reactions of CO2 + OH → HCO3
-(i) and barbituric acid →barbiturate anion + H + (ii) have been remeasured using as a new approach the pulse radiolysis technique with optical and conductivity detection. The rate constants obtained in the present study, ki (21 °C) = 6900 ± 700 M-1s-1 and kii (19 °C) = 22 ± 2 s-1 agree within experimental errors with values obtained earlier by other methods.
Synthesen mit aliphatischen Dialdehyden, XXXV. Synthesen mit 1- und 2-Adamantylmalonaldehyd/ Syntheses with Aliphatic Dialdehydes, XXXV. Syntheses with 1- and 2-Adamantyl Malonaldehyde
Authors: Reichardt Christian , Würthwein Ernst-Ulrich
Published: February 2015

The reaction of 1- (1) and 2-adamantyl malonaldehyde (2) with suitable electrophiles and nucleophiles yields adainantyl-substituted open-chain (3-5), carbocyclic (6) as well as heterocyclic compounds (7-19) with peculiar properties due to the presence of the lipophilic adamantyl group. The tetrazolo[1,5-a]pyrimidine (16) exhibits a solvent-dependent tetrazolo-azido valence isomerization reaction.
Synthesen von 3-Hydroxy-tetrahydrochinolin-2.4-dionen Syntheses of 3-Hydroxy-tetrahydroquinoline-2,4-diones
Authors: Stadlbauer Wolfgang , Kappe Thomas
Published: February 2015

Oxidation of 3-alkyl- and 3-arylsubstituted 4-hydroxy-2-quinolones (1) by irradiation with UV light, reaction with 3-chloro-peroxybenzoic acid or hydrogen peroxide in alkaline solution leads to 3-hydroxy-3-substituted quinoline-2,4-diones (2).