bluuebunny/crossref_metadata_2025 huggingface dataset:
EPR-Spektren von Tetrachlorocupraten verschiedener Aminothiazoliumderivate. Die Kristallstrukturen von 2-Amino-2-thiazolinium-und 2-Amino-4-methylthiazoliumtetrachlorocuprat(II) / EPR Spectra of Tetrachlorocuprates of Several Aminothiazolium Derivatives. The Crystal Structures of 2-Amino-2-thiazolinium and 2-Amino-4-methylthiazolium Tetrachlorocuprate(II)
Authors: Fernández Vicente , Morán Moisés , Doadrio Juan Carlos , Conradi Elke , Willing Wolfgang , Müller Ulrich
Published: March 2015

The tetrachlorocuprates. of the 2-aminothiazolium ion and of four of its substitution products, of 2-aminothiazolinium, and of 2-amino-4-carboxyl-thiazolidinium ions were prepared from the cor-responding heterocyclic bases, hydrochloric acid and copper(II) chloride in ethanol. The thermo-chromic compounds were characterized by their IR and electronic spectra. The EPR spectra of solutions, frozen solutions, and of the solids show the CuCl4
2- ion to have the structure of a flattened tetrahedron; in the case of some of the solids, distortions from D2d symmetry are observed. This was confirmed by two X-ray crystal structure determinations. Crystal data: 2-amino-2-thiazolinium tetrachlorocuprate, monoclinic, space group C2/c, a = 2772.8, b = 780.0, c = 1560.0 pm, β = 112.04°, Z = 8 (R = 0.047 for 2527 observed, independent reflexions); 2-amino-4-methylthiazolium tetrachlorocuprate, triclinic. P1̄, a = 780.4, b = 853.4, c - 1381.4 pm, α = 103.50, β = 99.39, γ = 104.17°, Z = 2 (R = 0.041 for 3319 reflexions). In both compounds the flattened CuCl4
2- tetrahedron is distorted and has two bond angles in the range between 130 and 141°. The heterocyclic cations are protonated at their ring N atoms; the corresponding H atoms and the H atoms of the amino groups are involved in N−H···Cl hydrogen bonding.
P3Se4I: 5-Iodo-2,3,6,7-tetraselena-1,4,5-triphosphabicyclo[221]heptan, ein neues Phosphorselenaiodid / P3Se4I: 5-Iodo-2,3,6,7-tetraselena-1,4,5-triphosphabicyclo[221]heptan, a New Phosphorus Selena Iodide
Authors: Blachnik Roger , Buchmeier Willi , Schneider Claudia , Wickel Ulrike
Published: March 2015

P3Se4I is formed by the reaction of molten P4Se3 and I2. P3Se4I is monoclinic, space group P21/c with the lattice parameters of a = 1130.3(3) pm, b = 654.5(2) pm, c =1420.5(4) pm, β - 117.64(2)°. d = 3.87 g cm-3 and dx = 3.82 g cm-3 for Z = 4. The structure of the molecule is derived from the structure of α-or β-P4Se3I2 by the substitution of a P−I group by a Se-atom. The P−I, P−P and Se−Se bond lengths are 249.9, 219.2 and 236.9 pm. resp. The mean P−Se bond length is 225.0 pm. The molecule is stabilized by two weak intramolecular P−Se and P−I bonds, comparable to the bonding situation in α-P4Se3I2 . The 31P NMR spectra reveal a coalescence effect, due to equilibrium between two isomeric forms of the molecules.
Phosphinsubstituierte Chelatliganden, XXIII [1] Darstellung und NMR-Spektren von Alkyl-arylphosphinothioformamiden, R(Ph)PC(S)NHMe / Phosphine-Substituted Chelate Ligands, XXIII [1] Synthesis and NMR Spectra of Alkyl-arylphosphinothioformamides, R(Ph)PC(S)NHMe
Authors: Kunze Udo , Tittmann Rolf
Published: March 2015

A series of alkyl-arylsubstituted N-methyl phosphinothioformamides, R(Ph)PC(S)NHMe (2 a-g), with varying bulkiness of the alkyl rest was synthesized from the racemic secondary phosphines 1a-g and methyl isothiocyanate. 1H and 13C NMR spectra of 2a−g reveal signal sets of diastereotopic nuclei due to the asymmetry of the molecule. The chemical shift and coupling constants were confirmed by simulation in case of 2b, c. The vicinal 31P−13C couplings of the menthyl and neomenthyl compounds 2f, g show an "anti-Karplus" behaviour (3J(gauche) > 3J(trans)) and allow the conformational assignment of the alicyclic group. The 31P chemical shifts of 2a−d give a linear correlation with the cone angle of the alkyl substituents quoted from literature.
Nb-Methyl Strictamine — A New Alkaloid from the Leaves of Rhazya stricta
Authors: Rahman Atta-ur- , Khanum Sajida , Badar Yasmin , Fatima Kaneez , Ahmad Yusuf
Published: March 2015

Continuing studies on the leaves of Rhazya stricta have resulted in the isolation of a new Picralima alkaloid, Nb -methyl strictamine 2.
Ein [1,3,4]Thiazaphospholidin, Darstellung und NMR-Daten / A [1,3,4]Thiazaphospholidine, Preparation and NMR Data
Authors: Heckmann Gernot , Fluck Ekkehard , Kuhm Peter
Published: March 2015

Preparation and properties of a [1,3,4]thiazaphospholidine are described. The 31P. 13C and 1H NMR spectra in double and triple resonance mode are recorded and discussed in detail.
Tritelluride mit komplexierten Kationen: Darstellung und Kristallstruktur von [Ba(en)3]Te3 und [Ba(en)4,5]Te3/ Tritellurides of Complex Cations: Synthesis and Crystal Structure of [Ba(en)3]Te3 and [Ba(en)4,5]Te3
Authors: Zagler Roland , Eisenmann Brigitte , Schäfer Herbert
Published: March 2015

The two title compounds have been prepared by reaction of appropriate mixtures of the elements in ethylenediamine. The structures have been determined on the basis of single crystal data. [Ba(en)3]Te3 crystallizes in the monoclinic system, space group P21/c with a = 918.0(4), b = 1203.7(6), c = 1639.9(6) pm, β = 93.4(1)°. In the structure there are bent tritelluride anions Te3
2- (bond lengths 273.9-278.5 pm, bond angle 105.7°). The Ba2+ cations are six coordinate by the bidentate ligand ethylenediamine. [Ba(en)4,5]Te3 crystallizes in the monoclinic system, space group Cc with a = 1752.8(6), b = 938.9(4), c = 3041.7(8) pm, β = 91.3(1)°. In this structure the bond lengths in the Te3
2- anions are shorter (272.1-273.1 pm, bond angles 110.9-112.2°). The cations are coordinated by four bidentate ligands, and are connected into pairs by a further ethylenediamine molecule. The resulting dinuclear [Ba(en)4]en[Ba(en)4]4+ units have the Ba2+ cations in CN 9.
Selbststapelnde Systeme, IV 2,3,7,8-Tetramethoxythianthreniumsalze/Selfstacking Systems, Part IV 2.3.7.8-Tetramethoxythianthrenium Salts
Authors: Hinrichs Winfried , Berges Peer , Klar Günter
Published: March 2015

By addition of solutions of nitrosyl hexachloroantimonate(V) in acetonitrile or of diiodine in n-hexane to a solution of 2.3.7.8-tetramethoxythianthrene (“Vn2S2”, 1) in toluene the oxidation products [Vn2S2][SbCl6] • CH3CN (2) and [Vn2S2]I3 (3), resp., are formed. Crystal structure determinations show both compounds to contain the [Vn2S2]+ ion. In contrast to the folded parent compound Vn2S2 its monocation [Vn2S2] T is planar, the short CS and CO distances (172-173 pm and 134-135 pm resp.) indicate an extended mesomeric system. Both compounds crystallize with segregated stacks of cations and anions. In 2 the coplanarly and equidistantly stacked [Vn2S2]+ ions have an A,B-sequence (distance between the planes of the ions 353 pm, intermolecular S···S distance 366 pm). In 3 the [Vn2S2]+ ions form dimers by SS contacts (S···S distance 316 pm); these dimers are arranged in a stair-like manner (distances between atoms of adjacent dimers 350-380 pm). The conductivities of 2 and 3 are 9.4 • 10-9 and 5.3 • 10-6 Sem-1 , resp.
Stereochemistry of Substituted Isomeric 3-Oxa-7-aza-bicyclo[3.3.1]nonan-9-ones
Authors: Küppers Horst , Hesse Karl-F. , Ashauer-Holzgrabe Ulrike , Haller Rolf , Boese Roland
Published: March 2015

Two isomers of 7-methyl-9-oxo-2,4-diphenyl-3-oxa-7-aza-bicyclo[3.3.1]nonan-1,5-ethyl dicarboxylate (1a and 1b) were obtained by condensation of 2,6-diphenyl-1-oxa-4-oxo-cyclohexan-3,5-ethyl dicarboxylate with methylamine and formaldehyde. Their crystal structures were determined by X-ray diffraction. They crystallize in the triclinic space group P1̄ with (for 1a) a = 12.907(5), b = 11.223(4), c = 8.993(4) Å, α = 105.82(4), β = 100.14(5), γ = 97.35(4)°, and (for 1b) a = 16.400(7), b = 13.062(4), c = 11.336(2) Å, α = 94.19(3), β = 94.74(3), γ = 102.56(4)°. This investigation has shown that isomer 1a has the boat-chair conformation, and isomer 1b has the chair-chair conformation. The formation of la causes a configurational change of the phenyl substituents. The two species are characterized by NMR spectroscopy. - Another comparable bicyclononanone with a bulky substituent at the nitrogen atom has been synthesized and was investigated spectroscopically. This compound should have chair-boat conformation (with the boat conformation in the N-heterocyclic ring) whereas 1a has the boat conformation in the O-heterocyclic ring.
X-Ray Crystal Structure Analysis of Deacetyldehydroeuphorianin: The Correct Structure of the Novel Pentacyclic Macrocyclic Diterpene, Euphorianin
Authors: Okogun Joseph I. , Fakunle Christopher O. , Ekong Donald E. U. , Lindner Hans J. , Habermehl Gerhard G.
Published: March 2015

The conversion of euphorianin to deacetyldehydroeuphorianin which was used in an X-ray crystal structure analysis is described. A new pentacyclic structure related to ingol tetraacetate is described for euphorianin.
Darstellung und Kristallstrukturen von LiGaCl4 und LiGaI4/ Preparation and Crystal Structure of LiGaCL4 and LiGaI4
Authors: Hönle Wolfgang , Hettich Bernhard , Simon Arndt
Published: March 2015

The crystal structures of LiGaCl4 and LiGaI4 have been determined by single crystal X-ray methods. Both compounds are isotypic with LiAlCl4 and characterized by LiX6 octahedra and GaX4 tetrahedra. Mean bond lengths are: d̄(Ga-X) = 217.4 pm (Cl) and 255.9 pm (I); d̄(Li-X) = 263.9 pm (Cl) and 305.3 pm (I), respectively. Common features of the isotypic compounds LiGaX4 (X = Cl, Br. I) are discussed.
Nitrido-Azido-Komplexe des Molybdän(VI): Synthese und Kristallstruktur von MoN(N3)2[HB(3,5-Me2pyz)3] und MoN(N3)Cl[HB(3,5-Me2pyz)3] / Nitrido Azido Complexes of Molybdenum(VI): Synthesis and Crystal Structure of MoN(N3)2[HB(3,5-Me2pyz)3] and MoN(N3)Cl[HB(3,5-Me2pyz)3]
Authors: Beck Johannes , Strähle Joachim
Published: March 2015

The reaction of MOCl4 (C2H5CN)2 with (CH3)3SiN3 and subsequent addition of Na[HB(3,5-Me2pyz)3] yields the nitrido azido complexes MoN(N3)2[HB(3,5-Me2pyz)3] and MoN(N3)Cl[HB(3,5-Me2pyz)3]. The two complexes crystallize from toluene as mixed crystals (space group P21/n, a = 1630.6, b = 878.0, c = 1675.5 pm, β = 112.67°, Z = 4). Crystallographic equivalent positions are occupied in a 4:1 ratio by diazido and monoazido monochloro complexes. The central Mo atom exhibits a sixfold coordination in form of a distorted octahedron with the nitrido ligand and one of the three pyrazol rings in axial positions. The triply bonded nitrido nitrogen atom (Mo≡N 164.2 pm) causes a strong trans effect, resulting in a long Mo-N6 bond (245 pm) to the trans positioned pyrazole nitrogen atom. The Mo-N distances in the equatorial plane are Mo-N2 215 and Mo-N4 216 pm, respectively. The nitrido complexes are remarkably stable against hydrolysis, probably due to steric shielding by the [HB(3,5-Me2pyz)3]- ligand. ν(Mo≡N) is observed at 1025 cm-1
closo-Halogenohydrohexaborate, II 11B-NMR-Spektren der closo-Halogenohydrohexaborate XnB6H6-n
2-, n = 0-6; X = Cl, Br, I / closo-Halogenohydrohexaborate, II 11B NMR Spectra of the closo-Halogenohydrohexaborates XnB6H6-n
2-, n = 0-6; X = Cl, Br, I
Authors: Fritze J. , Preetz W. , Marsmann H. C.
Published: March 2015

The point symmetries of the halogenohydrohexaborates within the nearly complete series XnB6H6-n
2-, X = Cl, Br, I; n = 1-5, are determined from the 11B and 11B{1H} NMR spectra, which show characteristic features for homologous isostructural compounds related to the electronegativity of the substituents. The chemical shifts are mainly influenced by -I, +M, and in the case of X = I by the heavy atom effect. Along with a strong antipodal effect a slight vicinal influence between neighbours in the B6 cage is observed, increasing with the number of substituted atoms
Gasphasen-Reaktionen, 59 [1, 2] Die Pyrolysen von Trifluormethylazid und Hexafluorazomethan / Gas Phase Reactions, 59 [1, 2] The Pyrolyses of Trifluoromethylazide and Hexafluoroazomethane
Authors: Bock Hans , Dammel R. , DesMarteau Darryl D.
Published: March 2015

Trifluoromethyl azide decomposes in a low-pressure flow system at rather high temperatures by splitting off N2. The nature of the resulting products depends largely on the wall material of the pyrolysis tube: using molybdenum above 1120 K, FCN is observed exclusively. Neither F2C=NF nor F3C-N=N-CF3 can be detected as intermediates by comparing their PE spectra with those continuously recorded while increasing the temperature. F3C-N = N - CF3 fragments already at 870 K to give N2 and F3C-CF3. The PE spectra of F3CN3 and F2C=NF are assigned based on MNDO calculations
Beiträge zur Chemie des Phosphors, 175 [1] Dinatrium-hexadecaphosphid: Darstellung durch Spaltung von weißem Phosphor mit Natrium / Contributions to the Chemistry of Phosphorus, 175 [1] Disodium Hexadecaphosphide: Preparation via Cleavage of White Phosphorus with Sodium
Authors: Baudler Marianne , Düster Doris
Published: March 2015

Disodium hexadecaphosphide has been prepared as a solvent adduct by reacting white phosphorus with sodium (atomic ratio 3 :1) in boiling tetrahydrofuran or monoglyme in the presence of 18-crown-6
The 2-Thioanalogues of tRNA Components Derived from 5-Hydroxyuridine
Authors: Małkiewicz Andrzej J. , Nawrot Barbara
Published: March 2015

The synthesis of 5-cyanomethoxy-2-thiouracil (5b) is described. The acid catalysed ethanolysis of 5b leads to 5-ethoxycarbonylmethoxy-2-thiouracil (5a). Condensations of 5-methoxy-2-thiouracil (5) and 5a with the sugar component 7 using the “silyl method” yield peracylated 5-methoxy-2-thiouridine (8) and 5-ethoxycarbonylmethoxy-2-thiouridine (8a), which under treatment with sodium methanolate/methanol afford title 5-methoxy-2-thiouridine (1) (s2mo5U) and 5-methoxycarbonylmethoxy-2-thiouridine (2) (s2mcmo5U), respectively
Darstellung und Schwingungsspektren von Chloro-Bromo-Ruthenaten(IV) einschließlich der Stereoisomeren / Preparation and Vibrational Spectra of Chloro-Bromo-Ruthenates(IV) Including Stereoisomers
Authors: Preetz W. , Allwörden H. N. v.
Published: March 2015

The mixed chloro-bromo complexes [RuClnBr6-n]2-, n = 1-5, have been separated for the first time by ion exchange chromatography on diethylaminoethylcellulose. Due to the stronger trans-effect of Br compared with Cl, on treatment of [RuBr6]2- with Cl- in the presence of Br2 nearly pure cis/fac-isomers,and by reaction of [RuCl6]2- withBr-/Br2 nearly purer tranS/mer-isomersforn = 2,3,4 are formed. The vibrational spectra of the mixed ligand complexes are completely assigned according to point groups D4h, C4v, C3v and C2v, respectively. The bands are observed in the characteristic regions: ν(RuCl): 340-270 > ν(RuBr): 245-190 > δ(ClRuCl) ≥ δ(ClRubr) ≥ δ(BrRuBr): 125-90 > νʟ: < 100 cm-1. The lower stability of the hexahalogeno complexes of Ru(IV), 4d, compared with the homologous complexes of Os(IV), 5d, is confirmed by a decrease of the force field constants by approximately 15%.
Ein- und zweikernige Bis(2,2′-bipyridyl)ruthenium-Komplexe mit N,O-Modelliganden für Dehydrogenase-Cofaktoren / Mono- and Binuclear Bis(2,2′-bipyridine)ruthenium Complexes with N,O-Ligands Modelling Dehydrogenase Cofactors
Authors: Ernst Sylvia , Kasack Volker , Bessenbacher Christian , Kaim Wolfgang
Published: March 2015

Coordination of substitutionally inert [Ru(bpy)2]2+ fragments (bpy: 2,2′-bipyridine) to the a-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (4) and 4,7-phenanthroline-5,6-dione (5) yields the complexes [(N,O-4)Ru(bpy)2]2⊕, [(O,O′-5⊖)Ru(bpy)2]⊕ and {(N,O; N′,O′-5)[Ru(bpy)2]2}4⊕ which exhibit a rich electrochemistry. The distinctly different electronic structures of the complexes are evident from the ESR behaviour of paramagnetic intermediates: N.O-coordinated complexes have the unpaired electron residing in the ligand n system upon reduction, albeit with g<2 for the binuclear complex of 5. The paramagnetic O,O′-coordinated mononuclear complex with 5 has its redox potentials shifted positively relative to that of the binuclear system. These results are particularly noteworthy because 4 and 5 can be regarded as model compounds for the flavin and methoxatin dehydrogenase cofactors.
Darstellung und Kristallstruktur des Bis((–)-strychninium)hexasulfids, (C21H23N2O2)2S6 / Synthesis and Crystal Structure of Bis((–)-strychninium)hexasulfide, (C21H23N2O2)2S6
Authors: Böttcher Peter , Buchkremer-Hermanns Heinz
Published: March 2015

Bis((-)-strychninium)hexasulfide has been synthesized from (-)-strychnine and (NH4)2S5 in ethanolic solution at 0 °C. It is monoclinic, S. G. C2, with a = 34.21(1) Å, b = 7.59(2) Å, c = 7.74(1) Å, β = 103.0(1)°. As expected, the S6
2--anions occur as unbranched zig-zag-chains. Surprisingly, they do not show the common helical all-trans-conformation but the all-cis-conformation. The cations and the anions are linked by hydrogen bridges, running from the terminal sulfur atoms of the polysulfide dianions to the protonated nitrogen atoms of the monoprotonated (-)-strychnine molecules.
Hydroxy! Radical-Induced Oxidation of Diisopropyl Ether in Oxygenated Aqueous Solution. A Product and Pulse Radiolysis Study
Authors: Schuchmann Man Nien , Sonntag Clemens von
Published: March 2015

In the radiolysis of N2O/O2(4:1 )-saturated aqueous solutions of diisopropyl ether(10-3 moldm-3), OH radicals abstract H-atoms, thereby producing radicals at C(2) (1 ≈ 78%) and to a lesser extent at C(l) (2 ≈ 22%) which are converted by oxygen into the corresponding peroxyl radicals 3 and 4. Some O2 radicals are formed by the reaction of radiolytically produced H atoms with oxygen. Methyl radicals formed in the course of the bimolecular decay of 3 and 4 give rise to methylperoxyl radicals 5. At high dose rate as delivered by 2.8 MeV electron pulses the products (G values in parentheses) are: isopropyl acetate (2.6), acetone (1.1), isopropanol (1.1), 2-isopropoxypropanal (1.4, estimated), formaldehyde (2.0), organic hydroperoxides (0.4), organic acids (0.5) and hydrogen peroxide (1.9). At low dose rates (≤ 0.39 Gy s-1 ) G(acetone) is considerably increased and is no longer balanced by an equivalent yield of isopropanol. This is thought to be due to an intramolecular H-abstraction of radical 3. Pulse radiolysis studies revealed that 3, 4 and 5 decay by second order kinetics. At the early stages the bimolecular decay is faster (2k ≈ 6 × 107 dm3mol-1s-1 ) than toward the end (2k ≈ 2 × 107 dm3moI-1s-1) . It is suggested that the faster decay at the beginning is due to a preponderance of termination by the primary peroxyl radical 4 with the tertiary peroxyl radical 3 while at later stages termination is mainly governed by the reaction of 3-1-3 which produces 5. The rate constants k(5 + 3) and k(5 + 5) are very likely much higher than 2k(3 + 3), hence 2k(3 + 3 ) < 2 × 107 dm3mol-1s-1 . In O2-saturated solutions O2 plays a considerable role in the termination reactions, and organic hydroperoxides which are unimportant in N2O/O2-saturated solutions at high dose rates are now the major products.
Mn3Nb6O11 und Mg3Nb6O11 - Darstellung von Einkristallen und Strukturverfeinerung / Mn3Nb6O11 and Mg3Nb6O11 - Preparation of Single Crystals and Structure Refinement
Authors: Burnus R. , Köhler J. , Simon A.
Published: March 2015

Dark green single crystals of Mg3Nb6O11 have been prepared by heating a pellet containing MgO, Nb, Nb2O5 (15:14:8) at 1550 °C in a Nb-container. Single crystals of the isotypic Mn3Nb6O11 were formed by heating a mixture of LiF, MnF2, Mn, NbO, NbO2 (1:1:1:1:2) in a corundum crucible at 750 °C. Both compounds crystallize in the trigonal space group P3̄ m 1 (Z = 1) with a = 6.041(1), c = 7.466(1) and a = 6.080(1), c = 7.627(1), respectively. The positional parameters for Mg3Nb6O11 are in excellent agreement with those determined by Marinder from powder data.
Alkoxohydridoaluminates. I 27Al NMR Characteristics of (C4 H9)4N+ AlH4-n(OR)n
- in Benzene
Authors: Heřmánek Stanislav , Fusek Jiří , Kříž Otomar , Čásenský Bohuslav , Černý Zbynĕk
Published: March 2015

The 27Al NMR spectra of (C4H9)4N+AlH4-n(OR)n
- prepared in the reaction of (C4H9)4NAlH4 with ROH (R = CH3, C2H5, i-C3H7, t-C4H9, n-C5H11, n-C9H19, cyclo-C6U11, C6H5, CH3OCH2CH2) in benzene show - in contrast to the Li+ and Na+ salts - a distinct H-splitting, which has allowed to ascertain: 1) the presence of all members (n = 0-4) in solution, 2) the Al chemical shift and AI -H coupling constant of all individual classes, namely (n = 0): 101.6 ppm, quintet 174 Hz; (n = 1): 114-123 ppm, quartet 184-193 Hz; (n = 2): 103-112 ppm, triplet 197-219 Hz; (n = 3): 75-91 ppm, doublet 218-237 Hz; (n = 4): 51-73 ppm, singlet, 3) increased shielding in the order: CH3 < n-R = i-R = sec-R < C6H11 ⪡ C6H5 < t-C4H9. The anomalous "sagging" pattern of the curve: δ27Al vs. number of OR groups, is interpreted on the basis of significant differences among Al and H and OR in electronegativity.
Darstellung, Kristallstruktur und Eigenschaften von β-Ga2Br4 / Preparation, Crystal Structure and Properties of β-Ga2Br4
Authors: Hönle Wolfgang , Simon Arndt , Gerlach Gabriele
Published: March 2015

The compounds Ga2Br4 (α+β) have been prepared by reacting GaBr3 with Ga metal without a solvent or in a hydrocarbon medium. α-Ga2Br4 is isotypic with Ga2Cl4, and β-Ga2Br4 with Ga2I4. Both forms have to be formulated as Ga+(GaBr4)- according to their crystal structures. The first order phase transition α→β has been investigated by means of DTA and temperature dependent X-ray powder photographs.

The crystal structure of β-Ga2Br4 has been refined with single crystal data (R3c; a = 2163.4(8) pm; c = 869.2(4) pm; Z = 18; R = 0.037). Main building units are GaBr4
- tetrahedra (d̄(Ga -Br) = 232.9 pm), connected in three dimensions by capped trigonal prisms (6+2+1) around Ga+. The crystal chemical relationships between β-Ga2Br4 and Ga2I4 are discussed.
Strukturbestimmung von Ga[GaCl4] und α-Ga[GaBr4] nach Kristallisation aus Halogenbenzolen / Structure Determination of Ga[GaCl4] and α-Ga[GaBr4] Crystallized from Halobenzene Solvents
Authors: Schmidbaur H. , Nowak R. , Bublak W. , Burkert P. , Huber B. , Müller G.
Published: March 2015

Single crystals of Ga[GaCl4] and α-Ga[GaBr4] have been obtained by crystallization from chlorobenzene and bromobenzene, respectively. The crystal structures of the two compounds, determined previously only on the basis of photographic data, were refined to a more satisfactory level of accuracy. The results confirm the presence of tetrahedral GaX4
- anions as thecounterions to dodecahedrally coordinated Ga+ cations. The gallium-halogen distances in these dodecahedral arrays fall into four classes, thus resulting in a significant asymmetry of the Ga(I) center. This deviation from ideal S4 symmetry is also apparent in the 69Ga NMR spectra of the crystalline powder samples. Approximate calculation of the data leads to asymmetry parameters (η) of 0.44 and 0.27 for the chloride and bromide, respectively. Crystal data Ga[GaCl4]: Pnna (#52), a = 7.200(1), b = 9.625(1), c = 9.498(1) Å; Z = 4. For α-Ga[GaBr4]: Pnna, a = 7.528(1), b = 9.972(1), c = 10.010(1) Å, Z = 4.
Al7Te10 — das erste Chalcogenid mit zweiwertigem Aluminium / Al7Te10 — the First Chalcogenide of Divalent Aluminum
Authors: Nesper Reinhard , Curda Jan
Published: March 2015

Al7Te10 is prepared from a melt of the elements in stoichiometric amounts in a corundum crucible contained in a sealed quartz ampoule. The ruby red cube shaped crystals are stable below 840 K. The structure of Al7Te10 (R32-D3
7 a = 1439.5 pm, c = 1793.2 pm, Z = 6, R = 0.03) is a distorted defect variant of a tetrahedral arrangement of the 4H-polytype. The central unit, a double barrelane [Te4Al4-Al4Te4], contains an Al -Al bond of 260 pm, which is somewhat longer (n = 0.83) than an expected single bond (250 pm, n = 1). This homopolar bond disturbs the electrostatically favorable (Al-Te-)n sequence in the structure which is compensated by the occurrence of four-membered Al2Te2 rings. Al7Te10 is a Zintl phase according to 1/2{[Al2+-Al2+][Al3+]12[Te2-]20} and exhibits semiconducting and diamagnetic behaviour.
Infrared, 57Fe Mössbauer, and 31P NMR Spectroscopic Characterization of Fe(CO)4L (L = Phosphine and Phosphite)
Authors: Inoue Hidenari , Nakagome Takashi , Kuroiwa Takeshi , Shirai Tsuneo , Fluck Ekkehard
Published: March 2015

A series of trigonal bipyramidal Fe(CO)4L complexes has been prepared and characterized by infrared, 57Fe Mössbauer and 31P NMR spectroscopy. A linear correlation, with a negative slope, between the CO stretching frequencies and the isomer shifts demonstrates that the triple bond nature of the carbonyl ligands is strengthened with increasing iron-to-phosphorus back donation. The linear dependence of the quadrupole splittings on the isomer shifts with a positive slope has revealed that the σ-donor capability of the phosphine or phosphite ligand is offset by the π-acceptor capability. The formation of Fe(CO)4L complexes from the corresponding free ligands is accompanied by a downfield shift of 31P NMR chemical shifts. The coordination shifts are linearly correlated with the Mössbauer isomer shifts.
Reaktion von Oxomolybdän-Komplexen mit Alkyldithiocarbazaten. Darstellung und Charakterisierung von Hydrazido- und Diazenido-Komplexen des Molybdäns / Reaction of Oxomolybdenum Complexes with Alkyldithiocarbazates. Synthesis and Characterization of Hydrazido- and Diazenido Complexes of Molybdenum
Authors: Mattes Rainer , Scholand Heinz , Mikloweit Ulrich , Schrenk Volker
Published: March 2015

(2).

The reaction of alkyldithiocarbazates NH2NHC(S)SR′ with MoO2(S2CNR2)2 R, R′ = Me, Et) yields the diazenido hydrazido complexes Mo(NNC(S)SR′)(NH2NC(S)SR′)(S2CNR2)2 (1), reaction with the molybdenum hydroxylamidate complex MoO2(ONMe2)2 gives the diazenidobis( hydrazido) complex Mo(NNC(S)SMe)(NH2NC(S)SMe)2(Me2NO)-CH3OH The crystal structures of 1 a (R = Me, R′ = Et) and 2 have been determined. The metal atoms in 1 a and 2 are seven coordinated and have MoN2S5 and MoN3O2S2 ligand arrays, respectively. Both compounds contain the approximately linear diazenido ligand NNC(S)SR in addition to one (1a) or two (2) N,S-chelating hydrazido(1-) ligands NH2NC(S)SR. When 1a is treated with HCl, the dimeric complex (Me2NCS2)(O)Mo(μ-NNC(S)SEt)2 Mo(S2CNMe2) (4) is obtained. X-ray crystallography showed 4 to be an asymmetric dinuclear complex, with a Mo-Mo distance of 267.2(1) pm. One Mo site has a square pyramidal MoOS2N2 geometry, while the other one has an approximately trigonal prismatic MoN2S4 geometry. The mean N-N distance in 4 is 135(1) pm. The reaction of NH2NHC(S)SMe with MoO2(acac)2 yields Mo(Me2CNNC(S)SMe)(NNC(S)SMe)(MeSC(S)NNC(S)SMe) (3). Its structure has been determined by X-ray crystallography. 3 contains a unique combination of three different N- and S-chelating ligands: the Schiff base Me2C=NNC(S)SMe, the highly bent bidentate diazenido ligand NNC(S)SMe (∡ Mo-N-N = 142.1(5)°), and the novel planar tridentate ligand MeSC(S)NNC(S)SMe. The latter can be taken as neutral diacyldiazene or, more likely, as the dianion of the as yet unknown MeSC(S)NH -NHC(S)SMe. The N - N distance in this ligand is 136.1(9) pm.
Reaktion von DioxomoIybdän(VI)-Komplexen mit O-Methyl-thiocarbazat Darstellung und Charakterisierung von Schiffbase-, Hydrazido- und Diazenido-Komplexen des Molybdäns / Reaction of Dioxomolybdenum(VI) Complexes with O-Methylthiocarbazate Synthesis and Characterization of Schiffbase, Hydrazido and Diazenido Complexes of Molybdenum
Authors: Mattes Rainer , Scholand Heinz , Mikloweit Ulrich , Schrenk Volker
Published: March 2015

trans

The reaction of NH2NHC(S)OR, (R = Me, Et) with MoO2(acac)2 yields the dimeric complexes MO2O3(MeC(O)CHC(Me)NNC(S)0R)2 (1) with the planar O = Mo - O - Mo = O group. The tetradentate O,N,S-donor ligand is formed through condensation of acetylacetone with the organohydrazine. The reactions of NH2NHC(S)OMe with MoO2(S2CNEt2)2 and MoO2(ONEt2)2 give the diazenido hydrazido complexes Mo(NNC(S)OMe)(NH2NC(S)OMe)(S2CNEt2)2·CH2Cl2
(2) and Mo(NNC(S)OMe)(NH2NC(S)OMe)2(ONEt2) (4). The metal atoms in both compounds are seven coordinated and contain the approximately linear diazenido ligand NNC(S)OMe and one (2) or two (4) N,S-chelating hydrazido(1-) ligands NH2NC(S)OMe. 2 has crystallographically imposed mirror symmetry. Recrystallization of 2 from toluene in air gives the asymmetric dinuclear complex (Et2NCS2)(O)Mo(μ-NNC(S)OMe)2Mo(S2CNMe2) (3). The Mo-Mo distance is 267.0(2) pm. One Mo site has square pyramidal MoOS2N2 geometry, the other trigonal prismatic MoN2S4 geometry. The coordination of the bridging N atoms is slightly pyramidal. The compounds 1, 2 and 3 have been further characterized by vibrational spectroscopy.
Synthesis and Photoelectron Spectroscopy of Spin Labeled Metal Complexes
Authors: Shen Dekang , Zhu Lizhi , Zhao Liangzhong
Published: March 2015

(4)

Two new spin labeled metal complexes; cobalt(II) bis(2,2,6,6-tetramethyl-1-oxyl-4-piperidyl p-salicylaldiminobenzoate) (3), copper(II) bis(2,2,6,6-tetramethyl-1-oxyl-4-piperidyl-p-salicylaldiminobenzoate) were prepared. The synthesis of amino derivatives of nitroxide compounds were improved by a simplified synthetic route. The XPS spectra of 3 and 4 were determined. The observed N Is, Cu 2p and Co 2p spectra of spin labeled metal complex are discussed.
Synthesis of Some New 2-Imino-2,3-dihydro-1,3,4-thiadiazole and Selenadiazole Derivatives
Authors: Abdelhamid Abdou Osman , Shawali A. S.
Published: March 2015

(2)

Diazotized 3(5)amino-5(3)-phenylpyrazole reacts with phenacylthiocyanate (1) and phenacylselenocyanate (10) to give the corresponding 1,3,4-thiadiazoline derivative (5) and 1,3,4- selenadiazoline derivative (12), respectively. A mechanism is proposed and it is substantiated by an alternate synthesis of 5 and 12 from the corresponding hydrazidoyl bromide (6) with potassium thiocyanate and potassium selenocyanate, respectively. The thiadiazoline (5) and selenadiazoline (12) give the respective N-acyl derivatives (7a) and (12) with acetic anhydride. Nitrosation of 5 and 12 gives the corresponding N-nitroso-derivatives (8a) and (14), respectively. Cyclization of 6 gives the corresponding 9 with triethylamine in benzene.
Darstellung und Kristallstrukturen von Ca4In2N und Sr4In2N
Authors: Cordier Gerhard , Rönninger Stephan
Published: March 2015

The new compounds Ca4In2N and Sr4In2N crystallize in the tetragonal system (space group I41/amd, No. 141). In and Ca together form a rocksalt structure. All octahedral holes, which are built by Ca only, are occupied by nitrogen. The In atoms form In-In zig-zag-chains; the In-In bond lengths are 316.4 pm (Ca compound) and 332.0 pm (Sr compound), resp.
Schwermetall-π-Komplexe II [1] Arenkomplexe des Quecksilbers(I)
Authors: Frank W. , Dincher B.
Published: March 2015

The crystalline compounds [(CH3C6H5)2Hg,][AlCl4]2 (1), [(1,2-(CH3)2C6H4)2Hg2][AlCl4]2(2), [(1,3,5-(CH3)3C6H3)2Hg2][AlCl4]2 (3), [1,2,4,5-(CH3)4C6H2Hg2][AlCl4]2 (4) and [((CH3)6C6)2Hg2][AlCl4]2-CH3C6H5 (5) have been prepared from mercury(I)chloride, aluminium trichloride and the corresponding arenes and characterized by elem ental analysis. The crystal structure of 5 has been determ ined from single crystal X-ray diffraction data and refined to R - 0.093 for 3269 unique reflections. Crystal data: monoclinic, space group P21/c, a = 2116(1), b = 1095.1(7), c = 1880(1) pm, β - 104,9(1)°, Z = 4. Each atom of a central Hg2 unit (Hg -Hg distance 251.5 pm) is asymmetrically complexed by hexamethylbenzene, the Hg - Carene distances being in the range from 241 to 340 pm. Two distorted AlCl4 tetrahedra complete a “molecular” [arene2Hg2][AlCl4]2 unit. The shortest Hg-Cl distances are 310 and 312 pm, respectively.
The Vibrational Spectra of NH4VO3 at Elevated Temperatures and Pressures
Authors: Heyns A . M. , Venter M. W. , Range K.-J.
Published: March 2015

Results obtained from the vibrational spectra of NH4VO3 and its deuterated analogues show that at least two types of hydrogen bond interactions can be identified at am bient conditions. In accordance with the structural data on NH4VO3 (F. C. Hawthorne and C. Calvo, J. Solid State Chem. 22, 157 (1977)) these interactions are assigned to normal, strong hydrogen bonds and weaker bifurcated ones, respectively. The temperature dependence of some of the N -H bands indicates that the normal hydrogen bonds decrease in strength with increasing temperatures, while the bifurcated ones tend to increase in strength. The NH4
+ ions do not show fluxional behaviour at ambient conditions and even the bifurcated hydrogen bonds are of the type that is dominated by acceptor strength of the anions and not by a volume effect. The Ram an active NH4
+ vibrations are very weak compared to the V - O modes and could not all be observed in the highpressure diamond anvil cell. The temperature dependence of the V - O Ram an active modes suggests that changes in the crystals of NH4VO3 brought about by the application of heat mainly involve the O -V -O angles, while pressure changes are mostly accommodated by changes in the V -O bridging bonds and O -V -O bridging angles.
Computerunterstützte mechanistische Analyse der Streith-Reaktion mit dem Programm RAIN
Authors: Fontain Eric , Bauer Johannes , Ugi Ivar
Published: March 2015

An improved version of the computer program RAIN (for bilaterally generating Reaction And Intermediate Networks from educts and products; FORTRAN 77, MS-DOS) is presented. Its application is illustrated by the elaboration of a network of mechanistic pathways for the Streith reaction.
Studies on Wasp Venom, II A New Mast Cell Degranulating Peptide from the Wasp Paravespula vulgaris
Authors: Schulze Uwe , Schrader Klaus-Dieter , Chen Robert , Grotjahn Lutz , König Wilfried A.
Published: March 2015

From the extract of 3991 venom glands of the most common European wasp species Paravespula

vulgaris a novel basic pentadecapeptide was isolated and investigated by amino acid analysis, micro-Edman-degradation and fast atom bombardment mass spectrometry. The peptide has the sequence H-Ile-Asn-Trp-Lys-Lys-Ile-Lys-Ser-Ile -lle -Lys-Ala-Ala-Met-Asn and exhibits strong mast cell degranulating activity similarly to the mastoparans isolated from various wasp species.
Synthese und Eigenschaften von Pentaazadienido-Komplexen des zweiwertigen Cobalts. Kristallstruktur von [Co(OCH3)(tolNNNNNtol)]6 · 2C9H12
Authors: Schmid Raimund , Beck Johannes , Strähle Joachim
Published: March 2015

Co(tolNNNNNtol)2 (1) is obtained from solutions of 1,5-di-p-tolyl-1,4-pentaazadiene und CoCl2 - 6H2O in aqueous ammonia. It is a paramagnetic, explosive, red com pound which reacts with alcohols to the alcoholates Co(OR)(tolNNNNNtol). The methoxy complex is hexameric. It crystallizes from mesitylene/methanol as [Co(OCH3)(tolNNNNNtol)]6 · 2C9H12 in the triclinic space group P1̄ with the lattice constants: a = 1667.1(5), b - 1784.2(5), c = 2159.2(6) pm, α = 93.05(3)°, β = 96.10(2)°, γ = 64.63(2)°, Z = 2. In the hexameric complex six Co atoms and six methoxy groups form a central twelve membered Co - O ring with a symmetry close to D3d. The pentaazadienide ligands act as additional bridges between two Co atoms, coordinating one Co atom monodentate with N1 and the other Co atom bidentate with N3 and N5. This leads to alternating tetrahedral and octahedral coordination of the Co atoms. The average Co-O distances are 192,3 pm in the CoO2N2 tetrahedron and 198,0 pm in the CoO2N4 octahedron. The corresponding Co-N distances are 206.3 and 221.4 pm respectively. In the planar N5 zigzag chain slightly elongated double bonds N1 - N2 and N4 -N5 of 128.2 pm and partial double bonds N2 -N3 and N3 -N4 of approximately 134.6 pm are observed.
Crystallographic Studies and Physicochemical Properties of π-Electron Systems, Part 7 Refinement of the Crystal and Molecular Structure of p-N,N-Dimethylaminobenzoic Acid, Full ab initio STO-3G Optimization of its Molecular Geometry, and Empirical Analysis of Substituent Effects on the Geometry of Benzene Rings in p-Substituted Benzoic Acids
Authors: Anulewicz R. , Häfelinger G. , Krygowski T. M. , Regelmann C. , Ritter G.
Published: March 2015

The crystal and molecular structure of N,N -dimethylaminobenzoic acid (DABA ) was redetermined by means of X-ray diffraction. Crystal data are: Mr = 165.2, triclinic, P1̄, a = 6.651(2) Å , b = 8.045(2) Å , c = 8.609(2) Å , α - 88.97(3)°, β = 94.72(3)°, γ = 113.76(3)°, V = 420.13 Å3, Z = 2, Dm = 1.28 g cm-1, Dx = 1.306 g cm-1; CuKα: λ = 1.54178 Å, μ = 6.74 cm -1, F(000) = 176.00, T - 293 K; R = 0.0684, Rw = 0.0780 for 1185 observed reflections. The DABA molecules are almost planar and form cyclic dimers exhibiting no orientational disorder with separation of oxygen atoms RO...O - 2.627(2) Å . The pattern of molecular geometry in DABA suggests a relatively strong through-resonance effect between the NMe2 and COOH groups and shows non-additivity of substituent effects on valence angles and bond lengths in the ring. Mesomeric equalization of CO bond lengths in the carboxylic groups of 10 well solved p-substituted benzoic acids is found to depend linearly on the RO...O distance in H-bridged dimers. Full abinitio STO -3G optimizations of molecular geometries for monomers of DABA , p-aminobenzoic acid, benzoic acid, and formic acid as well as for aniline and N,N -dimethylaniline show resonable agreement with experimental data. Changes of molecular geometries on formation of planar H-bridged dimers have been obtained from calculations for benzoic acid dimers, benzoic - formic acid complex, and formic acid dimers. The latter was also optimized using the 6 -31 G basis set.
Die Kristallstruktur von Bis(η-cyclopentadienyl)titana(Ti,IV)- cyclohexaselenan, Cp2TiSe5
Authors: Fenske Dieter , Adel Jörg , Dehnicke Kurt
Published: March 2015

Cp2TiSe5 has been prepared by the reaction of trim ethyltetradecylammonium-polyselenide with Cp2TiCl2 in ethanol solution and subsequent extraction of the dry residue with dichloromethane. Cp2TiSe5 crystallizes in the space group P1 with two formula units in the unit cell (2559 observed, independent reflexions, R = 0.074). The cell dimensions are a = 808.6, b = 822.6, c = 1190.7 pm, α - 96.28°, β - 106.06°, γ = 108.78°. The structure consists of discrete Cp2TiSe5 molecules with the TiSe5, ring in the chair conformation.
Die Kristallstruktur von Gd2B5/ The Crystal Structure of Gd2B5
Authors: Schwarz Christine , Simon Arndt
Published: March 2015

Gd2B5 is synthesized from Gd and B in the presence of GdCl3 as a flux. The compound crystallizes in the monoclinic space group P21/c with a = 713.6(1), b = 715.9(1), c = 718.3(1) pm and β =102.68(1)°. The structure consists of a 3-dimensional framework of Bft-octahedra and two types of B2-units enclosed in 32434-nets of Gd atoms. The different B -B-distances are discussed in terms of connectivity and Pauling bond orders.
Donor-Akzeptor-Komplexe von WCl3(N3S2) und WBr3(N3S2). Die Kristallstruktur von WCl3(N3S2) ·THF/ Donor Acceptor Complexes of WCl3(N3S2) and WBr3 (N3S2).The Crystal Structure of WCl3(N3S2)·THF
Authors: Khabou Abderraouf , Willing Wolfgang , Müller Ulrich , Dehnicke Kurt
Published: March 2015

The donor acceptor complexes WC13(N 3S2)-L (L = TH F, pyridine), and [WCl3(N3S2)]2 · dipy are prepared from WCl3(N3S2) and the corresponding donor molecules. WBr3(N3S2) ­ THF is formed by the reaction of WCl3(N3S2) THF with BrSiMe3. The complexes have been characterized by their IR spectra. The crystal structure of WCl3(N3S2) THF was determ ined by X-ray diffraction. It crystallizes monoclinically in the space group P21/c with four formula units per unit cell (1903 observed, independent reflexions, R = 0.031); the cell dimensions are a = 1072.0. b = 1007.2, c = 1128.9 pm; β = 94.84°. The tungsten atom is a member of a nearly planar WN3S2 ring with WN bond distances of 180 and 184 pm, which correspond to double bonds. The sixfold coordination of the W atom is completed by three chlorine atoms and the O atom of the tetrahydrofuran ligand, which is coordinated in trans-position to one of the N atoms; the THF molecules forms a dihedral angle of 40.1° with the WN3S2 ring.
Komplexe mit substituierten 2,5-Dihydroxy-p-benzochinonen: EA[C6(NO2)2O4] · H2O (EA = Ca, Sr)/ Complexes with Substituted 2,5-D ihydroxy-p-benzoquinones: EA [C6(NO2)2O4] · 4H2O(EA = Ca, Sr)
Authors: Robl Christian
Published: March 2015

Single crystals of EA[Q(NO2)2O4] · 4H2O (EA = Ca. Sr) were grown in aqueous silicagel. Ca2+ has CN 8. It is surrounded by 4 oxygen atoms of two bis-chelating [C6(NO2)2O4]2- ions and 4 water molecules, which form a distorted, bi-capped trigonal prism. Sr2+ is coordinated similarly, with an additional water molecule joining the coordination sphere to yield CN 8+1. Corrugated chains extending along [010] and consisting of EA2+ and nitranilate ions are the main feature of the crystal structure. Adjacent chains are interlinked by hydrogen bonds.
Chemische Effekte der Nitrosylsubstitution in hexakoordinierten Carbonylwolfram-Verbindungen/ Chemical Effects of Nitrosyl Substitution in Hexacoordinated Carbonyl Tungsten Complexes
Authors: Kundel P. , Berke H.
Published: March 2015

The reaction of mer-tricarbonyl-nitrosyl-bis(triisopropylphosphite)tungsten hexafluorophosphate (1a) with MeMgl or Bu4NI affords tricarbonyl-iodonitrosyl-(triisopropylphosphite)tungsten (2). Similarly, a carbonyl group of la can be replaced by a fluoride ion resulting in transdicarbonyl- fluoronitrosyl-bis(triisopropylphosphite)tungsten (3). Oxygen nucleophiles like OPh- , OCH3
- or OH- either substitute or attack a carbonyl group in la and cause formation of dicarbonyl-nitrosyl-bis(triisopropylphosphite)tungsten phenoxide. methoxide or formate derivatives (4, 5 or 7). respectively. Nitrite ions react with la under CO substitution and bind as nitro ligands to the tungsten center. Addition of equivalent amounts of MeLi, PhLi and NaBH4 to la leads to the formation of tricarbonyl-nitrosyl-(triisopropylphosphite)tungsten methyl and hydrido compounds (8a, 11a) as well as to dicarbonylnitrosyl-bis(triisopropylphosphite)tungsten methyl, phenyl and hydrido complexes (8b, 10 and 11b ) . In the presence of an excess of MeLi., la is transformed to a β-diketonate derivative 9.
Montanin G, Neo-Clerodane Diterpenoid from Teucrium montanum
Authors: Malakov Peter Y. , Papanov Georgi Y.
Published: March 2015

A new neo-clerodane diterpenoid, montanin G was isolated as a minor compound from the aerial parts of teucrium montanum var. scorpilii. Its structure 19.6α-diacetoxy-3β-hvdroxy- 4α . 18:15,16-diepoxy-neo-clerodane-13(16).14-dien-20.12R-olide was established by chemical and spectroscopic means and by correlation with teupireinin.
Metal Complexes with Tetrapyrrole Ligands, XLV. The Mercuration of Nickel(II), Palladium(II), and Platinum(II) Porphyrins
Authors: Buchler Johann W. , Herget Gerhard
Published: March 2015

The mercuration of 5,10,15,20-tetrakis(4-methylphenyl)porphyrin complexes M(TTP)** (2a-c; M = Ni, Pd, Pt) is described. Treatment of Ni(TTP) (2a) with mercuric acetate in refluxing benzene and subsequently with aqueous sodium chloride yields a mixture of species M(TTP-HgnIn) (1 < n < 3) from which the monomercurial, Ni(TTP-HgCl) (3a) is isolated in 35% yield after silica chromatography. A more rapid reaction occurs with mercuric trifluoroacetate in chlorobenzene. With this system, Pd(TTP-HgCl) (3b) and Pt(TTP-HgCl) (3c) along with their bis-, tris-, and tetrakis-mercurated analogs are obtained. The reaction times indicate that replacement of NiII by PdII and PtII progressively diminishes the rate of electrophilic attack at the porphyrin periphery, consistent with a decrease of the total density of negative charge on the porphyrin ligand in these complexes.
Synthese und Thermolyse von α-Titanocenyl-substituierten Dimethylethern: die überraschende Bildung von [(CH3Cp)Ti(OCH3)Cl]4/ Syntheses and Thermolysis of a-Titanocenyl-Substituted Dimethylethers: the Unexpected Formation of [(CH3Cp)Ti(OCH3)Cl]4
Authors: Erker Gerhard , Krüger Carl , Schlund Rüger
Published: March 2015

Reaction of the Grignard-Reagent ClMgCH2OCH , (2) with (RCp)2TiCl2 (5a) (R = H). 5b (R = CH,) yields the titanocene(methoxymethyl)chlorides (RCp)2Ti(Cl)CH2OCH3, 7a and 7b. Thermal decomposition of 7b (2 min, 110 °C in toluene) yields the paramagnetic titanium (III) complex [(CH3Cp)Ti(OCH3)Cl]4 (8) in addition to the organic products ethylene and dimethvlether. The tetranuclear complex 8 crystallizes in space-group P21/n with a = 9.125(2), b = 8.899(1), c = 20.226(2) Å and β - 92.804(9)°. In 8 the Ti4-core is alternatingly doubly-bridged by μ-chloro- and μ-methoxy ligands.
[Ni5(SEt)10] und [Ni4(SC6H11)8], homoleptische Nickel-Thiolate mit pentagonal-prismatischen und cubanartigen Schwefelgerüsten /[Ni5(SEt)10] and [Ni4(SC6H11)8], Homoleptic Nickel-Thiolates with Pentagonal-Prismatic and Cubane-Like Sulfur Frameworks
Authors: Kriege Michael , Henkel Gerald
Published: March 2015

NiCl2 reacts with NaSR in methanol solution to give the black diamagnetic complexes [Ni5(SR)10] (R = Et, 1) and [Ni4(SR)8] (R = C6H11 , 2). Crystals of 1 are monoclinic, space group P21/h with a = 13.149(4), b = 15.571(4), c = 17.917(5) Å , β = 105.31(2)° and Z = 4. 2 crystallizes from methylene chloride with sixteen solvent molecules per unit cell in the orthorhombic space group Ibca with a = 17.902(8), b = 18.289(8), c = 37.99(2) Å and Z = 8. The structures of 1 and [Ni4(SC6HM)8] · 2 CH 2Cl2 (3) have been determined by X-ray crystallography and refined to R(RW) = 0.072 (0.062) and 0.119 (0.128), respectively. Both complexes are cyclic neutral molecules and contain square planar NiS4 coordination sites (1: mean Ni - S 2.200 Å , mean S -Ni -S 81.8 ( 2 x ) . 98.3 ( 2 x ) , 170.8° ( 2 x ) ; 2: mean Ni - S 2.213 Å , mean S - Ni - S 80.9 (2 x ) , 98.2 ( 2 x ) , 167.5°(2 x )) condensed via opposite edges. A s a result, prismatic sulfur frameworks are observed which are pentagonal in the case of 1 and tetragonal in the case of 2. Their lateral faces are centered by Ni atoms. The symmetry of the Ni-S core portion approaches D5h for 1 and D4h for 2. With reference to the toroidal N i-S frameworks, the sulfur-carbon bonds of each pair of opposite ligands are in axial and equatorial positions, respectively. This configuration alternates around the prismatic sulfur arrangement which is completely compatible with the even number of nickel atoms present in 2, but results in a node for 1 due to the five-fold symmetry.
Modellreaktionen zur Plumbagin-Synthese, 1. Mitteilung Monoaminoalkylierung von 1,5-Naphthalindiol und anschließende Hydrogenolyse / Model Reactions for Plumbagin Synthesis, 1st Communication Monoaminoalkylation of 1,5-Naphthalinediol with Following Hydrogenolysis
Authors: Möhrle Hans , Folttmann Hubertus
Published: March 2015

1,5-Naphthalinediol yields with a secondary amine and formaldehyde under special conditions the mono Mannich base. Following hydrogenolysis with palladium charcoal results in 2-methyl- 1,5-naphthalinediol.
Synthesis of a B-Lymphocyte Activating α-Methylserine Containing Lipopentapeptide
Authors: Metzger Jörg , Olma Aleksandra , Leplawy Miroslaw T. , Jung Günther
Published: March 2015

The lipopentapeptide S-[2,3-bis(palmitoyloxy)-[2-R,S]-propyl]-N-palmitoyl-[R]-cysteinyl-[ R|- α-methylseryI-[R]-α-methylseryl-[S]-asparaginyl-[S]-alanine (Pam3Cys-α-MeSer-α-MeSer-Asn -Ala) has been synthesized as an analogue of the immunoadjuv- ant Pam3Cys-Ser-Ser-Asn -Ala (TPP) via fragment condensations. The two [R]-α-methylserine residues were introduced instead of [L]-serine in order to obtain a mitogenic lipopeptide resistant against proteases. As the parent lipopeptide TPP the analytically pure analogue with McSer was found to induce enhanced cell proliferation of spleen lymphocytes.
1:1-Salze des organischen Donors Tetra(methylthio)tetrathiafulvalen und Bis(maleonitriIdithiolato)-Komplexen: (TTM-TTF)+[Ni(mnt)2]- und (TTM-TTF)+[ Pt(mnt)2]- / 1:1 Salts of the Organic Donor Tetra(methylthio)tetrathiafulvalene and Bis(maleonitriledithiolate) Complexes: (TTM -TTF)+[Ni(mnt)2]- and (TTM -TTF)+[Pt(mnt)2]-
Authors: Brunn Karl , Endres Helmut , Weiss Johannes
Published: March 2015

(TTM-TTF)+[Ni(mnt)2]- and (TTM-TTF)+ [Pt(mnt)2]- {TTM-TTF = Tetra(methylthio)tetra- thiafulvalene. mnt = maleonitriledithiolate} were obtained as products of the reactions of TTM-TTF with [Et4N][Ni(mnt)2] and [Et4N][Pt(mnt)2]. (TTM-TTF)+ [Ni(mnt)2]- is tridinic. P1, a = 7.650(2), b = 9.671(3). c = 9.846(4) Å. α = 103.47(3)°, β = 101.76(3)°, γ = 91.73(3)°, V = 6913 Å. Z = 1, dc = 1.75 g cm-3. For the isomorphous (TTM-TTF)+[Pt(mnt)2]- a = 7.749(2). b = 9.684(4). c = 9.883(3) Å, α = 103.31(2)°,β = 102.54(2)°, γ = 91.43(3)°, V = 702 Å3 Z= 1, dc = 2.04 g cm-3. The structures consist of mixed stacks of the organic radical cations and of bis(maleonitriledithiolato)metal(III) anions.