bluuebunny/crossref_metadata_2025 huggingface dataset:
Preparation and Spectroscopic Properties of the [Re2(C3S4Se)5]2- Anion Complex and Electrical Conductivities of the Oxidized Species [C3S4Se2- = 1,3-Dithiole-2-selone-4,5-dithiolate(2-)]
Authors: Maikawa Takashi , Nakano Motohiro , Arakawa Ryuichi , Matsubayashi Gen-etsu , Mori Wasuke
Published: February 2015

The dinuclear rhenium(IV) complexes with the C3S4Se-ligand [1,3-dithiole-2-selone-4,5- dithiolate(2-)], [PPh4]2- (1) and [NEt4]2[Re2(C3S4Se)5] (2), were prepared. Complex 2 was oxidized by a reaction with [Fe(C5H5)2][PF6] or [TTF]3[BF4]2 (TTF·+ = the tetrathiafulvalenium radical cation) and by the current-controlled electrolysis to yield [NEt4]x[Re2(C3S4Se)5] (x = 0.15 and 0.5) and [TTF][Re2(C3S4Se)5]. The compounds exhibit electrical conductivities of 3.3 x 10-3 - 9.3 x 10-4 S cm-1 for compact pellets at room temperature. Electrochemical and spectroscopic properties of the complexes are discussed on the basis of cyclic voltammetry and ESR, XPS and IR spectra as well as the magnetic susceptibility of the TTF salt.
Metallorganische Lewis-Säuren, LV [1] Darstellung und Reaktionen von Tetracarbonylmethyltetrafluoroboratoosmium, cis-(OC)4Os(FBF3)CH3/Organometallic Lewis Acids, LV [1] Preparation and Reactions of Tetracarbonylmethyltetrafluoroboratoosmium, cis-(OC)4Os(FBF3)CH3
Authors: Rosendorfer Philipp , Mihan Shahram , Niemer Burkhard , Beck Wolfgang
Published: February 2015

The reaction of cis-Me2Os(CO)4 with HBF4·Et2O affords the complex cis- (OC)4Os(FBF3)CH3 (2). The coordinated tetrafluoroborate of 2 is easily substituted by H2O, [Re(CO)5]-, [Re(CO)4(CN)CH3]- (from Re(CO)5CH3 and NaN(SiMe3)2), SCN- and PPhMe2 to give neutral or cationic complexes 4-6, 8, 9, respectively. The structure of cis-H3C(OC)4Os- Re(CO)5 has been determined by X-ray diffraction.
Die Kristallstruktur von RbCuSe4/ The Crystal Structure of RbCuSe4
Authors: Klepp Kurt Otto , Weithaler Claudia
Published: February 2015

Crystals of RbCuSe4 are orthorhombic, oP24, s.g. P 212121 (No.19), Z = 4 with a = 5.541(2) Å, b = 8.814(2) Å , c = 13.277(9) Å. The crystal structure was determined from diffractometer data and refined to a conventional R of 0.019. RbCuSe4 is a pseudo-one-dimensional compound, characterized by infinite polyanionic chains 1
∞-[CuSe4]-. The atomic arrangement corresponds to that of α-NH4CuS4.
Synthese und Röntgenstrukturanalyse von KCuGd2Mo4O16 und KCuTb2Mo4O16/Synthesis and X-Ray Analysis of KCuGd2Mo4O16 and KCuTb2Mo4O16
Authors: Müller-Buschbaum Hk. , Gallinat St.
Published: February 2015

Single crystals of the so far unknown compounds KCuGd2Mo4O16 (I) and KCuTb2Mo4O16 (II) have been prepared by flux technique. The compounds crystallize with monoclinic symmetry. space group C6
2h-C2 /c with (I): a = 5.278(2), b = 12.666(5), c = 19.604(14) Å; β = 92.76(6)°; (II): a = 5.259(13), b = 12.616(3), c = 19.556(9) Å, β = 92.93(4)°, Z = 4. Molybdenum exhibits tetrahedral coordination. The surroundings of copper can be described by distorted tetrahedra, capped by two more distant oxygen atoms, and the rare earth ions show a square antiprism. Potassium is inside an irregular polyhedron. The relationship of the structures of (I) and (II) is discussed with respect to the KLnMo2O8 type compounds. Coulomb term calculations of the lattice energy indicate an oxidation state of copper higher than CuI.
Photodegradation of EDTA and NTA in the UV / H2O2 Process
Authors: Sörensen Martin , Frimmel Fritz H.
Published: February 2015

The influence of H2O2 on the UV degradation of the broadly used aminopolycarboxylates EDTA and NTA in aqueous solution was investigated. The photochemical degradation in the UV /H2O2 process was compared with classical oxidative treatment of potable water. The German drinking water regulation (Trinkwasserverordnung) was the orientation for all experiments. The Advanced Oxidation Process (AOP) turned out to be superior to the classical oxidation processes. The photochemical degradation of EDTA and NTA by UV irradiation could be significantly stimulated in the presence of H2O2. There was a strong increase in the degradation rate and a decrease in the quantum yield of the aminopolycarboxylates. Experiments with butyl chloride as radical scavenger proved the photolytically generated hydroxyl radicals to be responsible for the increase in the degradation rates.

The effect of increasing the degradation rate at higher concentrations of H2O2 was limited, because the steady-state concentrations of the hydroxyl radicals as reactive species, did not increase at the same rate as the initial concentration of H2O2.

Low amounts of iron dissolved from the high-grade steel photoreactor walls had a significant catalytic effect on the degradation.
Die Kristallstrukturen von 1,4-Dimethylpiperazinium-tetrabromocobaltat(II) und -zinkat(II), (dmpipzH2) [MIIBr4] (M = Co, Zn) / The Crystal Structures of 1,4-Dimethylpiperazinium Tetrabromocobaltate(II) and -Zincate(II), (dmpipzH2) [MIIBr4] (M = Co, Zn)
Authors: Feist Michael , Trojanov Sergej , Kemnitz Erhard
Published: February 2015

The compounds (dmpipzH2)[MIIBr4] (M = Co, Zn) crystallize at room temperature from equimolar solutions of 1,4-dimethylpiperazine and MBr2 · n H2O in 3M HBr. (dmpipzH2)[CoBr4] is isotypic with the homologous chlorometalates of Co and Zn and crystallizes in the mono­ clinic space group P21/m with a = 6.424(3), b = 14.588(6), c = 7.102(6) Å, β = 90.87(6)°, Z = 2. (dmpipzH2)[ZnBr4], however, crystallizes in the monoclinic space group P21/c with a = 7,605(5), b = 13,760(9), c = 13,286(7) Å, β = 93,03(6)°, Z = 4. Both structures contain centrosymmetric cations (dmpipzH2)2+ in the chair form and slightly distorted tetrahedra [MBr4]2- with a mirror plane in the case of M = Co. Several distances N···Br in both structures are interpreted in terms of N-H···Br hydrogen bonds which are favoured by the packing in the case of M = Zn.
Polysulfonylamine, LXX [1]. Das Assoziat EtOH ··· OH2 als Bindeglied in einem quaternären 18-Krone-6-Neutralmolekül-Komplex: Bildung und Kristallstruktur von (CH2CH2O )6·2 H2O·2EtOH · 2HN(SO2Ph)2 / Polysulfonylamines, LXX [1] The EtOH --OH2 Entity as a Link in a Quaternary 18-Crown-6 Complex with Uncharged Molecules: Formation and Crystal Structure of (CH2CH2O )6·2 H2O·2EtOH · 2HN(SO2Ph)2
Authors: Henschel Dagmar , Blaschette Armand , Jones Peter G.
Published: February 2015

Di(benzenesulfonyl)amine, 18-Crown-6, Quaternary Complex of Uncharged Molecules, Crystal Structure Co-crystallization of 18-crown-6 (18C6) and di(benzenesulfonyl)amine from dry ethanol at -20 °C affords the thermally labile and structurally uncharacterized ternary complex 18C6·2EtOH·2HN (SO2Ph)2 (2). Single crystals of the quaternary complex 18C6-2 H2O·2EtOH·2HN(SO2Ph)2 (1) were fortuitously obtained by repeated recrystallization of a sample of 2 from ethanol that was not kept completely dry. The crystal packing of 1 (triclinic, space group P1̄) is built up from isolated formula units displaying crystallographic inversion symmetry and pseudo D3d symmetry of the crown ring. The water molecules are located on opposite sides of the ring plane. Each H2O is connected to two OC atoms of the crown separated by a [CH2CH2OCH2CH2] segment (OWH···OC 210 and 208 pm, angles at H 169 and 164°), and accepts an O-H···Ow hydrogen bond from an ethanol molecule (H···OW 176 pm, angle 177°).
Crystal Structure and Magnetic Susceptibility of Ce8Pd24Sb
Authors: Gordon Robert A. , DiSalvo Francis J.
Published: February 2015

The ternary compound Ce8Pd24Sb is very close in composition to the intermediate valent binary CePd3. A single crystal study yielded a cubic cell with a = 8.461 (1)Å, Pm3̄m symmetry with wR2 = 0.0412 based on 1453 reflections (222 unique) and 16 parameters. This new structure type is composed of distorted perovskite and Cu3Au subcells arranged with the perovskite-like units centred on the corners of the cube. Fitting the magnetic susceptibility data above 100K to a Curie-Weiss expression yielded a Weiss constant of -15(3)K (antiferromagnetic) and an effective high temperature moment per cerium of 2.45(4)/μв indicating trivalent cerium. No ordering was observerd above 3K.
Mehrkernige Oxo-Vanadium- und Oxo-Molybdän-Komplexe mit dem Dianion der Quadratsäure als Brückenligand. Strukturen von [C(NH2)3]4[V2O2F4(C4O4)2]·4H2O, [nBu4N]4[V3O3F4(C4O4)3]·2H2O, [Et4N]3[Mo3O8F(C4O4)2], [Et4N]4[Mo4O10F6(C4O4)] und [ Et4N]3[Mo2O3Cl3(C4O4)2] / Polynuclear Complexes of Oxo-Vanadium and Oxo-Molybdenum with the Dianion of Squaric Acid as Bridging Ligand. Crystal Structures of [C(NH2)3]4[V2O2F4(C4O4)2]·4H2O, [nBu4N]4[V3O3F4(C4O4)3]·2H2O, [Et4N]3[Mo3O8F(C4O4)2], [Et4N]4[Mo4O10F6(C4O4)] and [ Et4N]3[Mo2O3Cl3(C4O4)2]
Authors: Hilbers Martin , Meiwald Margita , Mattes Rainer
Published: February 2015

Aqueous or methanolic solutions containing vanadium(IV), molybdenum(V) and molyb-denum(VI) oxo species and fluoride ions react with squaric acid to give the oligonuclear complexes [C(NH2)3]4[V2O2F4(C4O4)2]·4H2O (1), Cs4[V3O3F4(C4O4)3]·5H2O (2a), [nBu4N]4[V3O3F4(C4O4)3]·2H2O (2b), [Et4N]4[Mo4O10F6(C4O4)] (3a), [Et4N]4[Mo4O10Cl6(C4O4)] (3b), [Et4N]3[Mo3O8F(C4O4)2] (4) and [Et4N]3[Mo2O3Cl3(C4O4)2] (5). The structures of compounds 1, 2a, 2b, 3a, 4 and 5 have been determined by single crystal X-ray diffraction. The [V2O2F4(C4O4)2]4- ion in 1 consists of the planar V2O2F4 core with the vanadium sites bridged by two ,μ-1,2-squarato ligands. The unique cone-shaped [V3O3F4(C4O4)3]4- ion in 2a and 2b contains a central defect and severely distorted V3F4 cubane unit. Each vanadium atom bears a terminal oxo ligand; pairs of vanadium atoms are bridged by μ-1,2-squarato ligands. The [Mo4O10F6(C4O4)]4- ion in 3a consists of a squarate ion, which is coordinated to four metal centers. Pairs of metal atoms are bridged by μ(O)μ(F)-bridges. Two terminal oxo ligands and one terminal fluoro ligand complete the metal coordination. Oxo and fluoro ligands are partly disordered. The structure of the [Mo3O8F(C4O4)2]3- ion in 4 is related to the structure of [V3O3F4(C4O4)3]4- It consists of a defect Mo3(O3F) cubane unit. Two pairs of molybdenum atoms are bridged by μ-1,2-squarato ligands. Terminal oxo and dioxo groups complete the molybdenum coordination. The [Mo2O3Cl3(C4O4)2]3- ion in 5 exhibits a unique structure with a planar OClMo(μ-O)(μ-Cl)MoOCl core and a cis, cis-orientation of the oxygen ligands. Two, μ-1,2-squarato ligands bridge the molybdenum centers above and below the Mo2O3Cl3 plane.
Molekülstrukturen von Tautomeren des Benzoylaceton-benzoylhydrazons / Moleculare Structures of Tautomeric Forms of Benzoylacetone Benzoylhydrazone
Authors: Kraudelt Heide , Ludwig Eberhard , Schilde Uwe , Uhlemann Erhard
Published: February 2015

By crystallization from benzene two tautomeric forms of benzoylacetone benzoylhydra­ zone were isolated side by side. They were found to be the pyrazoline(III) and the enhydrazine(II) form. Crystal data: II: a = 9,247(2) Å , b = 9,953(2) Å , c = 16,112(4) Å , α = 81,79(1)°, β = 82,74(1)°, γ = 89,94(2)°; space group P1; Z = 4; R = 0,0584; 6197 unique reflexions; III; a = 17,357(6) Å, b = 21,190(7) Å , c = 7,908(5) Å; space group Pccn; Z=8; R = 0,0553; 1152 unique reflexions.
First Synthesis of C-Phenyl N-tert-Butyl [15N]nitrone (PBN-15N) for the EPR Spin Trapping Methodology
Authors: Zhang Yong-Kang
Published: February 2015

As compared to normal PBN, about fifty percent increase of electron paramagnetic resonance (EPR) spin trapping sensitivity has been gained by using a new 100% 15N-enriched spin trap, C-phenyl N-tert-butyl[15N]nitrone (PBN-15N). PBN-15N has been prepared by a convenient four-step route using ammonium-15N chloride as the starting material. This synthetic method produces 2-methyl-2-[15N]nitropropane which is useful for the synthesis of many other PBN-15N type spin traps for the purpose of increasing spin trapping sensitivity. EPR spin trapping with PBN-15N in benzene and in phosphate buffer has been investigated. The 15N hyperfine splitting constant (15N-hfsc) is larger than 14N-hfsc by 40%. The larger 15N-hfsc gives more opportunity to identify different radical addends within the same system.
Intramolekular-stabilisierte Organogallium-und -indiumhalogenide. Ein erstes neutrales Indiumhydrid
Authors: Kümmel Christoph , Meller Anton , Noltemeyer Mathias
Published: February 2015

The intramolecularly coordinating 2-(dimethylaminomethyl)phenyl-(X) and 4-terr-butyl-2,6-bis(dimethylaminomethyl)phenyl-(Y) ligands were employed in the preparation of the gallium and indium halides: X2InI (B), XInI2 (1), X2InBr (2), XInBr2 (3), XIn(Et)I (4), XGaI2 (6) and YInI2 (7). The first neutral indium hydride X2InH (5) was made in situ from LiInH4 and 2. Z2InCl (8) (Z = 2-pyridyl-bis(trimethylsilyl)methyl), and X3Ga (C) were also synthesized. The compounds are characterized by N. M. R. (1H, 13C, 29Si and for 6 71Ga) and mass spectrometry and elemental analyses or peak matching M. S.. N. M. R.-data are discussed as well as the X-ray structure analyses provided for B, 2, 4, 5, 7 and 8.
Ein Cadmium-Kupfer-Phosphat mit einfach überkappten trigonalen CdO6-Prismen-Netzen: Cd1.35Cu1.65(PO4)2
Authors: Münchau S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Cd1.35Cu1.65(PO4)2 have been prepared by solid state reactions below the melting point of the starting compounds. The light green crystals crystallize with monoclinic symmetry, space group C5
2h-P21/c , a = 9.062(2), b = 11.669(2), c = 5.950(2) Å , β = 97.88(2)°, Z = 4. Cd1.35Cu1.65(PO4)2 shows relationship to the mineral graftonite. The crystal structure is characterized by nets of corner connected Cd2O12 polyhedra. One point position is statistically occupied by Cd2+ and Cu2+ ions.
Primäre und sekundäre Ethyl-und i-Propylsulfoniumsalze sowie Kristallstruktur von i-C3H7SH2
+SbF6
- [1]
Authors: Minkwitz Rolf , Lohmann Ulrike , Preut Hans
Published: February 2015

The synthesis of salts of the type RnSH3-n
+MF6
- (R = C2H5, i-C3H7; n = 1, 2; M = As, Sb) by protonation of the corresponding thiols and sulfides in the superacid systems HF/MF5 is reported. The salts have been characterized by vibrational and NMR spectroscopic methods. Isopropylsulfonium hexafluoroantimonate is the first known example of a sulfonium salt, for which a SH bond distance has been determined by a crystal structure analysis, i-C3H7SH2
+SbF6
- crystallizes in the monoclinic space group P21/m with a = 568.0(4), b = 801.1(6), c = 1019.7(8) pm, β = 82.63(6) °, with two formula units per unit cell.
(1,3-Diethyl-1,3-dihydro-4,5-dimethyl- 2H -imidazol-2-yliden)-diiodtellur(II) [1]
Authors: Kuhn Norbert , Kratz Thomas , Henkel Gerald
Published: February 2015

The carbene adduct 5 is formed from the 2-tel-luroimidazoline 4 and iodine. The X-ray structure analysis reveals a dimeric structure in the solid state.
Zur Kenntnis eines Barium-Lanthanoid-Aluminat-Zinkats: BaLuAlZn3O7 mit einem Anhang zu Ba2Er2Zn8O13/On a Barium Rare Earth Aluminate Zincate: BaLuAlZn3O7 with a Note on Ba2Er2Zn8O13
Authors: Rabbow Ch. , Müller-Buschbaum Hk.
Published: February 2015

Reactions of BaCO3, ZnO, Lu2O3 and Al2O3 mixtures at temperatures up to 1500 °C led to small and colourless rods of BaLuAlZn3O7. The new compound crystallizes with hexagonal symmetry, space group C6v
4 -P63mc, a = 6.273, c =10.161 Å, Z = 2. In spite of small differences in the oxygen content BaLuAlZn3O7 is isotypic to Ba2Ln2Zn8O13. The crystal structure shows Zn2+ with tetrahedral, Lu3+ with octahedral and Ba2+ with anticuboctahedral coordination by O2-. It has been shown that parts of the [Zn3AlO7]5- network are fragments of the ZnO structure. In consequence one oxygen atom is fourfold coordinated by zinc/aluminium. The space group of Ba2Ln2Zn8O13 must be corrected to C6v
4 -P63mc.
1,4-Addition of Lithium Organyls to para-Quinols / Structure Determination of 2,6-Di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one
Authors: Henes Gerhard , Rieker Anton , Neumayer Markus , Hiller Wolfgang
Published: February 2015

Addition of lithium organyls to sterically hindered para-quinols leads to 1,2-or 1,4-adducts. The 1,4-addition prevails, if the 4-substituents in the quinol and the organic group in the lithium organyl are large. Four 1,4-addition products (2-cyclohex-2-en-1-ones) are synthesized and their structures investigated by NMR spectroscopy. The aryl groups at C-4 and C-5 acquire equatorial positions, the alkyl group at C-6 is bisectional. These results are confirmed by X-ray analysis of 2,6-di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1 -one, revealing a twist boat conformation of the cyclohexene ring.
Electrochemistry of Oxygenation Catalysts, Part 6 Electrosynthesis, Structure, Analytical and Electrochemical Properties of Monomeric [CoIII(salen)(DMF)2]+ X- Salts (X = PF6, ClO4)
Authors: Gollas Bernhard , Speiser Bernd , Stahl Hartmut , Sieglen Jürgen , Strähle Joachim
Published: February 2015

[CoIII(salen)(DMF)2]+ X- salts [X = PF6, ClO4; salen = bis(salicyliden)ethylendiiminato; DMF = dimethylformamide] have been synthesized by electrochemical and chemical (air) oxidation of CoII(salen). Their monomeric structure with two DMF molecules in the axial positions in both the solid state and DMF solution is shown by X-ray crystal structure analysis, thermal analysis, mass spectroscopy, and 1H and 13C NMR spectroscopy. The electrochemical reduction of the [CoIII(salen)(DMF)2]+ cation is investigated by cyclic voltammetry and com­ pared to the oxidation of the neutral CoII(salen). The redox reaction connecting the cobalt(II) and the cobalt(III) species appears to be a quasi-reversible electron transfer. These properties make the [CoIII(salen)(DMF)2]+ X-salts starting materials for the analysis of the interaction of basic substrates with cobalt(III) species in the context of the biomimetic oxygenation reactions catalyzed by such complexes.
Reduktion cyclischer Maleinsäurederivate/Reduction of Cyclic Maleic Acid Derivatives
Authors: Stachel Hans-Dietrich , Schachtner Josef , Seidel Josef
Published: February 2015

A series of potentially cytotoxic α,β-unsaturated γ -hydroxy-butyrolactones, -lactams and -thiolactones has been synthesized via regioselective hydride reduction of the appropriate maleic acid anhydrides, imides and thioanhydrides. By this means a straightforward access to naturally occurring antibiotic narthigenine 2, its hitherto unknown thio-analogue 5b and higher substituted derivatives and analogues of 2 is presented.
[Mn(n-Bu)(NPEt3)]4, eine manganorganische Verbindung mit Heterocuban -Struktur [Mn(n-Bu)(NPEt3)]4, an Organomanganese Compound with Heterocubane Structure
Authors: Mai Hans-Joachim , Neumüller Bernhard , Dehnicke Kurt
Published: February 2015

[Mn (n- Bu)(NPEt3)]4 has been prepared by the reaction of [MnBr(NPEt3)]4 with n-butyllithium in boiling pentane. The pyrophoric compound forms red, moisture sensitive crystals, which were characterized by IR spectroscopy and by a crystal structure determination (tetragonal, space group 141/a, Z = 4, structure solution with 699 observed unique reflections, R = 0.054. Lattice dimensions at -50 °C:a = b = 2177.4(3) pm, c = 1147.1(2) pm). [Mn (n-Bu)(NPEt3)]4 forms a nearly perfect Mn4N4 hetero cubane framework with μ3-N bridges of the NPEt3
- groups and σ-bonded n-butyl groups with Mn - C distances of 216.8 pm. The n-butyl groups and two of the ethyl groups are disordered.
Zur Kristallstruktur von ( Cu ,Mn )3,66Mo3O12/On the Crystal Structure of (Cu ,Mn)3,66Mo3O12
Authors: Sedello O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of (Cu,Mn)3.66Mo3O12 have been prepared in sealed copper tubes. X-ray investiga­tions lead to orthorhombic symmetry, space group D2h
16-Pnma, a = 5.1541(9), b = 10.788(2), c = 18.114(3)) Å , Z = 4. (Cu,Mn)3.66Mo3O12 is iso­typic to NaCo2.31Mo3O12 and (Cu,Co)3.75Mo3O12 with split positions for two of the metals.
Zur Kenntnis von Ba6Pr2Co4O15 und Ba5SrPr2Co4O15 On Ba6Pr2Co4O15 and Ba5SrPr2Co4O15
Authors: Müller-Buschbaum Hk. , Ünsal H.
Published: February 2015

Ba6Pr2Co4O15 (I) and Ba5SrPr2Co4O15 (II) have been prepared by high temperature CO2-LASER techniques. Both compounds crystallize with hexagonal symmetry, space group C6v
4 P63mc, (I): a = 11.814(1), c = 7.100(2) Å ; (II): a = 11.646(1), c = 6.8602 Å , Z = 2. It is remarkable that the strongly reducing Pr3+ can coexist with the more oxidizing Co3+.
Subsolidus Phasenbeziehungen in den Systemen MgGa2S4-MgCr2S4 und MgGa2S4-MgIn2S4 / Subsolidus Phase Relationships in the Systems MgGa2S4-MgCr2S4 and MgGa2S4-MgIn2S4
Authors: Haeuseler H. , Cordes W.
Published: February 2015

The title systems have been investigated on samples quenched at 700, 800 and 1000 °C. Five new compounds have been obtained and characterized by X-ray powder diffraction: Spinel type MgGa0.2Cr1.8S4, two compounds crystallizing in the olivine structure, MgGaCrS4 and MgGaInS4, and two layered materials, MgGa1.5Cr0.5S4 and MgGa1.5In0.5S4. Lattice para­ meters and phase widths of the compounds are given.
Synthese and Krystalchemie der β-Form eines gemischten Zinkorthoarsenats: Zn2,28Mg0,72(AsO4)2 / Synthesis and Crystal Chemistry of the β-Form of a Mixed Zinc Orthoarsenate: Zn2.28Mg0.72(AsO4)2
Authors: Frerichs D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Zn2.28Mg0.72(AsO4)2 have been prepared by CO2 LASER techniques. The compound crystallizes with monoclinic symmetry space group C5
2h-P21/n and the lattice parameters a = 5.292(2), b = 8.450(3), c = 7.737(3) Å , β = 96.33(3)°, Z = 2. Zn2.28Mg0.72(AsO4)2 is isotypic to β-Zn3(AsO4)2. The formation of the β-Zn3(AsO4)2 struc­ture instead of other possible orthoarsenates is discussed.
K+ auf einer mit Ca2+ unterbesetzten Punktlage in Ca3( VO4)2: Ein Beitrag über KCa10V7O28 / K+ at an Deficient Ca2+ Point Position in Ca3( VO4) 2: On KCa10V7O28
Authors: Schrandt O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of K Ca10V7O28 have been prepared by crystallization from flux. The yellow-green crystals show rhombohedral symmetry (trigonal space group C6
3V-R3c, a = 10.830(1), c = 37.860(1) Å , Z = 6). The differences of the crystal chemistry are discussed with respect to the isotypic compound Ca3(VO4)2. K+ replaces exclusively Ca2+ ions at one deficient point position.
Darstellung und Lithiumteilstruktur von Lithiumnitridtribromid, Li6NBr3 und Lithiumnitridtriiodid, Li6NI3 / Preparation and Lithium Sublattice of Lithium Nitride Trihalides, Li6NHal3 (Hal = Br, I)
Authors: Marx Rupert , Mayer Hans Michael
Published: February 2015

Single phase Li6NBr3 was prepared by the reaction of Li3N and dry, OH-free LiBr at 450°C. It is the most bromide rich compound in the quasi binary system Li3-2xN1-xBrx. The crystal structures of Li6NBr3 and of isotypic Li6NI3, have been redetermined from neutron powder diffraction data. Both compounds crystallize in the cubic space group Fm3m (No. 225), a(Li6NBr3) = 894.18(7), a(Li6NI3) = 951.7(1) pm with 4 formula units per unit cell. The anion sublattice comprises a rock salt like arrangement of N with one of the three halogen atoms (Hal1), with the remaining halogen atoms in the resulting N4Hal4 cubes. The structure may be regarded as an ordered AX3 variation of a body-centered packing. The lithium atoms are disordered over the 96 (distorted) tetrahedral NX3 holes in such a way that of the four neighbouring, face-sharing NBr3 tetrahedra along an N-H all-connection line only one is occupied. The resulting Li coordination polyhedron around N (and Hal1) is a distorted octahedron with 6 equidistant Li atoms. Hal2 is surrounded by 12 Li atoms. The Li6NHal3 structure may be regarded as an anti-form of the cryolite structure.
Darstellung, 11B-, 13C-, 1H-NMR- und Schwingungsspektren von μ-Methylen-bis-hexahydro-closo-hexaborat, [B6H6(CH2)B6H6]2-, und Kristallstruktur von [As(C6H5)4]2[B6H6(CH2)B6H6]· ½(CH3)2CO / Preparation, 11B- , 13C-, 1H NMR and Vibrational Spectra of μ-Methylene-bis-hexahydro-doso-hexaborate, [B6H6(CH2)B6H6]2- and Crystal Structure of [As(C6H5)4]2[B6H6(CH2)B6H6]· ½(CH3)2CO
Authors: Lübbe W. , Preetz W.
Published: February 2015

By reaction of [B6H6]2- with dibromomethane in acetonitrile μ-Methylene-bis-hexahydro-closo-hexaborate, [B6H6(CH2)B6H6]2-, is formed which can be separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of [As(C6H5)4]2[B6H6(C H2)B6H6] · (CH3)2CO has been determined by single crystal X-ray analysis: triclinic, space group P1 with a = 10.779(2), b = 10.8003(12) and c = 23.077(3) Å, a = 99.147(10), β = 91.569(13) and y = 91.288(11)°. The 11B NMR spectrum reveals the features of a monosubstituted octahedral B6 cage. The 13C NMR spectrum exhibits a multiplet at -5.44 ppm. In the 1H NM R spectrum a singlet of the methylene protons at 0.23 ppm and two singlets at 1.97 and -4.52 ppm of the BH fragments are observed. The IR and Raman spectra exhibit strong CH stretching bands between 2873 and 2762 cm-1, BH stretching bands between 2443 and 2403 cm-1, and a BC stretching vibration at 1138 cm-1 in the Raman spectrum.
Circular Dichroism Studies on New Optically Active 1,5-Benzodiazepine Derivatives
Authors: Khan Khalid Mohammed , Malik Farnaz , Hasan Mashooda , Perveen Shahnaz , Frelek Jodwiga , Snatzke Günther , Voelter Wolfgang
Published: February 2015

From thirty three new optically active 1,5-benzodiazepine derivatives the UV and CD data are reported and the bands discussed related to corresponding electronic transitions respectively stereochemical features.
Zur Reaktivität des Silaethens Me2Si=C(SiMe3)2: Regioselektivität, Stereoselektivität und relative Geschwindigkeiten von En-Reaktionen [1] / On the Reactivity of Silaethene Me2Si=C(SiMe3)2: Regioselectivity, Stereoselectivity and Relative Rates of Ene Reactions [1]
Authors: Wiberg Nils , Wagner Susanne
Published: February 2015

Ene reactions of Me2Si=C(SiMe3)2 (1) with propene or with methyl derivatives of propene and 1,3-butadiene, respectively, of the formula R 1 CH=CR2-CH2R3 take place regioselectively, as well as stereoselectively and are retarded by increasing bulk of R1, R3 (for example H < CH3 < CH=CH2 < CH=CHMe), as well as accelerated by an increasing tendency of R2 to donate electrons (for example H < CH3 ≈ CH=CH2 < CH2SiMe2[CH(SiMe3)2]). It is concluded from these studies, that ene reactions of 1 occur concerted and are HOMOene-LUMOenophile controlled.
Über die Reaktion von KPPh2 mit Fe(CO)5 und Fe(CO)4CS; Molekülstruktur von [(CO)4FePPh2]- / On the Reaction of KPPh*, with Fe(CO)5 and Fe(CO)4CS; Molecular Structure of [(CO)4FePPh2]-
Authors: Petz Wolfgang , Weller Frank
Published: February 2015

Fe(CO)5 reacts with [PPh2]- in THF at -78 °C to give the adduct [(CO)4FeCOPPh2]- (3) which decomposes at elevated temperature to give [(CO)4FePPh2]- (1), [Fe2(CO)8]2- (2) and (Ph2P)2 probably via a radical mechanism. Attempts to transfer 3 with the electrophiles MeSO3CF3 or Me3SnCl into the corresponding carbenes have failed and Fe(CO)5 along with Ph2PMe and Me3SnPPh2, respectively, are formed. 1 adds one equivalent of CS2 to generate [(CO)4FePPh2CS2]- (4). The [K-18-Krone-6] salt of 1 crystallizes in the triclinic space group P 1̄ with the unit cell parameters a = 929.5(2), b = 1112 .1(2), c = 2017.9(4) pm, α = 100.29(3)°; β = 94.07(3) °; γ = 114.58(3) °. The existence of 3 is established by low temperature 31P NMR spectroscopy.
A-Pr2S3, D-Ho2S3 und E-Yb2S3:Synthese und Einkristallstrukturuntersuchungen / A-Pr2S3, D-Ho2S3 and E-Yb2S3:Synthesis and Single Crystal Structure Investigations
Authors: Schleid Thomas , Lissner Falk
Published: February 2015

The oxidation of reduced chlorides (MCl2) or chloride-hydrides (MClHx) of the lanthanides with sulfur (700-850 °C, 7 d, sealed tantalum capsules or evacuated silica vessels) usually results in the formation of the sesquisulfides M2S3 as the main products. In the presence of appropriate fluxes (e.g., alkali halides), the products often are obtained as single crystals, and the flux decides which modification is favoured. Ternary halides of the trivalent lanthanides with the corresponding alkali metal can mostly be found as the second components. Crystal growth and structural investigations of thus produced single crystals of Pr2S3 (from PrClH0.67 + S + NaCl, 5:5:1, A type: orthorhombic, Pnma (No. 62), Z = 4, a = 748.22(5), b = 405.51(3), c = 1560.74(9) pm, R = 0.024, Rw = 0.020), Ho2S3, (from U - Ho2S3, + KI, 1:1, D type: monoclinic, P21/m (No. 12), Z = 6, a = 1746.15(9), b = 400.23(3), c = 1012.43(6) pm, β = 98.529(4)°, R = 0.041, Rw = 0.035), and Yb2S3 (from T-Yb2S3 + KI, 1:1, E type: trigonal, R3̄c (No. 167), Z = 6, a = 674.97(2), c = 1820.11(9) pm, R = 0.019, Rw = 0.018) are reported here. In accordance with the lanthanide contraction, the trivalent cations (M3+) exhibit sulfur coordination numbers of 7 and 8 in A -Pr2S3, 6 and 7 in D -Ho2S3, and 6 in E -Yb2S3 (corundum-type structure).
Polynuclear Gold(I) Complexes of Mercaptocarboxylic Acids
Authors: Sladek Alexander , Schneider Wolfgang , Angermaier Klaus , Bauer Andreas , Schmidbaur Hubert
Published: February 2015

In a search for air-stable and water-soluble mercapto compounds of gold with a high gold content, benzylthiol, a-m ercapto-acetic acid, β-mercapto-propionic acid, and thiosalicylic acid were converted into aurated sulfonium salts by treatment with reagents of the type [(R3P)Au]3O+ BF4
- or [(R3)P)Au]+ BF4
-. - BzSH served as a mono-functional model thiol, which was converted into BzS[Au(PMe3)]2
+ BF4
- (1). The small tertiary phosphine was chosen in order to minimize steric effects. In the crystal the cations are associated into centrosymmetrical dimers through short Au-A u contacts (auriophilicity). - The two carboxylic acids with thiol functions, HSCH2COOH and HSCH2CH2COOH, gave triply aurated species of the type {[(Ph3P)Au]2S(CH2)nCOOAu(PPh3)}+ BF4
- (2: n = 2, 3; n = 3). The crystal structure analysis of the representative compound 2 showed again the presence of centrosymmetrical cation dimers with geometrical details of the sulfonium part of the molecules very similar to those of the reference compound 1. In addition, the carboxyl groups in 2 and 3 bear a (phosphine)gold unit mono-hapto bound at one of the oxygen atoms. -2-HS-C6H4-COOH was converted into a sulfonium salt {[(Ph3P)Au]2S-C6H4-COOH}+ BF4
- (4), which crystallizes free of solvent from dry dichloromethane, and as a monohydrate with one mole of dichloromethane (4a = 4 H2O-CH2CI2) from hydrous CH2CI2. In the solvent-free crystalline phase (4) the cations are associated into dimers with the usual intermolecular double A u-A u contacts, but in 4a there are monomeric cations with the water molecule hydrogen-bonded to the carboxylic acid function
Phosphonio-substituierte 1,3-Diphosphanaph thaline aus der a,o-Kondensation von Phosphonium-benzyliden / Phosphonio-Substituted 1,3-Diphosphanaphthalenes from the α.o-Condensation of Phosphonium-benzylides
Authors: Jochem Georg , Schmidpeter Alfred
Published: February 2015

Triphenylphosphonium 1-trimethylsilylbenzylides 1 react with the bis(dichlorophosphino)- substituted ylide 2 both at their 1- and ortho-position to yield 1,3-diphosphatetraline derivatives 4 containing two ylide and PCI units each as alternating ring members. The two PCI groups differ decisively in their spontaneous dissociation in a polar medium, as well as in their oxidation by elemental sulfur. With gallium trichloride dicationic 1,3-diphosphanaphthalenes (1,3-benzodiphosphinines) are formed, in which both phosphorus ring members achieve twocoordination and which represent a novel π10 system
Hochdrucksynthese und Kristallstruktur von Nd4Au2O9 und Gd4Au2O9 / High Pressure Synthesis and Crystal Structure of Nd4Au2O9 and Gd4Au2O9
Authors: Steiner Claudia , Andratschke Martina , Range Klaus-Jürgen
Published: February 2015

Single crystals of Nd4Au2O9 and Gd4Au2O9 have been prepared by oxidizing mixtures of gold metal and Nd2O3 or Gd2O3, rsp., with KO2 under high-pressure high-temperature conditions (40 kbar, 1200°C) in a modified Belt-type apparatus. The X-ray structure analyses have been carried out on twinned crystals. The compounds crystallize in the orthorhombic space group Pbcn (Nd4Au,O9: a = 11.938(7) ,b = 6.126(2),c = 11.928(3) A ,Z = 4,1 = 0.0443; Gd4Au2O9: a = 11.922(2), 6 = 6.1242(7), c = 11.917(2) A, Z = 4. R1 =0.0232).

The title compounds are isostructural with La4Au2O9. Their structure comprises isolated square-planar AuO4 groups, stacked along [010] to form a columnar structure. The Au-Au distance along the columnar direction is 3.10 Å. Structural relations to Bi2CuO4 und (Nd, Pr)2AuO5 are discussed
Zwei monokline Kupfer-Oxovanadate des Magnesiums mit geordneter Metallverteilung: m-Mg2CuV2O8 und MgCu2V2O8. Ein Beitrag zur Dimorphie von Mg2CuV2O8 / Two Monoclinic Copper Oxovanadates of Magnesium Showing Ordered Metal Distribution: m-Mg2CuV2O8 and MgCu2V2O8. A Contribution on Dimorphism of Mg2CuV2O8
Authors: Schrandt O. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of ra-Mg2CuV2O8 (I) and MgCu2V2O8 (II) have been prepared by solid state reactions. The orange (I) and dark red (II) crystals show monoclinic symmetry, space group C5
2h -P21/c, (I): a = 6.167(3), b = 8.172(5), c = 6.400(8) Å, β = 116.22(3)°, Z = 2; (II): a = 6.453(1), b = 8.342(2), c = 11.517(2)Å,β 90.44(2), Z = 4. Both compounds show ordered metal distributions and vanadium in tetrahedral coordination by oxygen. (I) is characterized by elongated CuO6 octahedra and (II) by trigonal CuO5 bipyramids. m-Mg2CuV2O8 is the low temperature form of the formerly investigated orthorhombic o-Mg2CuV2O8. Calculations of the Coulomb parts of the lattice energy of the two crystal forms are discussed
1,1-Organoboration of Trimethyl-l-propynyltin Using Diorganoboryl-Substituted Ferrocenes
Authors: Wrackmeyer Bernd , Dörfler Udo , Milius Wolfgang , Herberhold Max
Published: February 2015

The reactions of various diorganoborylferrocenes, Fc -BR2 [1, R = Me (a), Et (b), iPr (c), tBu (d), Ph (f), R2B = 9-borabicyclo[3.3.1]nonyl (e)] and 1,1′-bis(9-borabicyclo[3.3.1]nonyl)- ferrocene (2) with trimethyl-l-propynyltin (3) were studied, and the products of the 1,1- organoboration were characterized as the alkenyltin compounds 4 -6 by 1H, 11B, 13C and 119Sn NMR. In the cases of 1a - 1d and If, there is competition between the transfer of a ferrocenyl group and the other organyl groups R from boron to carbon, whereas in the case of the 9-borabicyclo[3.3.1]nonane derivatives 1e and 2, the enlargement of the bicyclic system takes place selectively (compounds 4e and 6). The molecular structure of the product 6, obtained from the reaction between the 1,1′-diborylated ferrocene 2 and two equivalents of 3, was determined by single crystal X-ray analysis (space group P21/c monoclinic; Z = 4, a = 958.3(2), b = 1610.4(3), c = 2405.3(5) pm and β = 90.33(3)°)
Preparation and Structure of Poly(gold)telluronium Salts
Authors: Angermaier Klaus , Schmidbaur Hubert
Published: February 2015

Tris[(triphenylphosphine)gold(I)]telluronium tetrafluoroborate (1) was prepared from the corresponding oxonium salt and bis(t-butyldimethylsilyl)tellurium in dichloromethane at -78°C. The product forms yellow crystals, thermally stable to 125°C. It was identified by standard analytical and spectroscopic techniques, including a single crystal X-ray diffraction study. In the crystal lattice, the cations form tellurium-capped triangles of gold, which are associated into dimers through short intermolecular Au -Au contacts, resembling those in the corresponding sulfur and selenium compounds. - The reaction of (t-BuMe2Si)2Te with four equivalents of [(Ph3P)Au]BF4 in tetrahydrofuran at -78°C gives a tetranuclear compound, {[(Ph3P)Au]4Te}2+ 2 BF4
- (2) which differs from 1 in its analytical and spectroscopic data. Its structure could not be determined, but it is assumed that the dications have a square pyramidal geometry
Synthese und Kristallstruktur von Pb2LnAl3O8 (Ln = Eu, Gd) / Synthesis and Crystal Structure of Pb2LnAl3O8 (Ln = Eu, Gd)
Authors: Werner J.-P. , Müller-Buschbaum Hk.
Published: February 2015

Single Crystals of Pb2LnAl3O8 (Ln = Eu, Gd) have been prepared by flux techniques. The compounds crystallize with cubic symmetry, space group Oh-Pn3̅m, a(Eu) = 9.4578(5), a(Gd) = 9.4448(7) Å, Z = 4. The crystal structure is characterized by heterocubane units of the type Pb4O4 and hexagonal bipyramids of oxygen around the rare earth ions. These components form a network made of macro polyhedra of the type Pb4O4- LnO6- Pb4O4
Synthese und Kristallstruktur von manganhaltigen Pyroboraten: MnCo(B2O5) und MnMg(B2O5) / Synthesis and Crystal Structure of Manganese Containing Pyroborates: MnCo(B2O5) and MnMg(B2O5)
Authors: Utzolino Anne , Bluhm Karsten
Published: February 2015

The compounds MnCo(B2O5) (I) and MnMg(B2O5) (II) were prepared by using B2O3 flux techniques in an argon atmosphere. X-ray investigations on single crystals showed triclinic symmetry, space group Ci
1 - P1̄, I: a = 320.94(10), b = 619.20(11), c = 939.0(2) pm, a = 104.38(2)°, β = 90.76(2)°, γ = 92.046(14)° and II: a = 318.97(7), b = 619.8(2), c = 936.7(2) pm, α = 104.47(2)°, β = 90.60(2)°, γ = 91.98(2)° Z = 2. Their structures are isotypic with Co2(B2O5). All metal ions are octahedrally coordinated by six oxygen atoms. The structures contain diborate anions B2O5
4-. Each boron atom is threefold coordinated by oxygen.
Darstellung und Charakterisierung von N(CH2PPh2)3, N(CH2PPh2)3Mo(CO)3 und [HN(CH2PPh2)3Mo(CÖ)3]BF4 / Preparation and Characterisation of N(CH2PPh2)3,N(CH2PPhi)3Mo(CO)3 and [HN(CH2PPh2)3Mo(CO)3]BF4
Authors: Walter Olaf , Hüttner Gottfried , Kern Rainer
Published: February 2015

The synthesis of N(CH2PPh2)3 (1) and its spectroscopic properties are reported. Reaction of N(CH2PPh2)3 with (CH3CN)3Mo(CO)3 leads to N(CH2PPh2)3Mo(CO)3 (2). The cationic complex [HN(CH2PPh2)3Mo(CO)3]+ (3) is obtained by protonating the N atom of 2 with aqueous HBF4. The spectroscopic and structural properties of 2 and the cation 3 are compared. The results indicate an interaction of the ligand N atom and the Mo atom through space over more than 350 pm. It is shown from IR data that 2 is fixed on silicagel by hydrogen bonding.
, der erste einzähnig koordinierte Aziridin-Komplex / , the First Mono-Coordinate Aziridine Complex
Authors: Beckerath Stephan von , Lorenz Ingo-Peter , Fawzi Riad , Steimann Manfred
Published: February 2015

The photolytically induced CO-substitution reaction of CpMn(CO)3 with N-benzyl-aziridine leads to the first mono coordinate aziridine complex,

. It is stable against thermal C2H4 elimination up to 135°C. No nitrene complexes {Cp(CO)2Mn}nNBz (n = 1, 2) were detected.

The X-ray structure analysis of

shows the intact three-membered ring ligand and the pyramidal configuration of the nitrogen atom.
Synthese und spektroskopische Untersuchungen von Nickelkomplexen mit substituierten Dibenzotetraaza[14]. Annulenliganden Synthesis and Spectroscopic Studies on Nickel Complexes with Substituted Dibenzozetraaza[14] Annulenes
Authors: Schumann Hans
Published: February 2015

A series of diamagnetic macrocyclic nickel complexes I bearing substituted dibenzotetraaza[14] annulene ligands with methyl and/or phenyl groups on NCR moieties and methyl or nitro groups on the phenylen units have been prepared by Ni template synthesis from the correspon­ding 1,3-diketo- and 1,2-diamino-benzene components. 1H and 13C NMR data are reported and interpreted in terms of sterical and electronical changes induced by these substituents upon the ligand and compared with results of theoretical calculations. Further characterisation is based on IR, UV/Vis and mass spectroscopic measurements.
Darstellung und Kristallstruktur von [P(C6H5)4]2[2-SnCl(C6H5)2B10H9] / Preparation and Crystal Structure of [P(C6H5)4]2[2-SnCl(C6H5)2B10H9]
Authors: Nachtigal C. , Preetz W.
Published: February 2015

By reaction of [N(C4H9)4]2[B10H10] with chlorotriphenyltin in acetonitrile at 70°C the 2- (chlorodiphenyltin)-decaborate anion [2-SnCl(C6H5)2B10H9]2- is formed and can be separated from the starting compound by ion exchange chromatography on diethylaminoethyl (DEAE) cellulose. The X-ray structure of [P(C6H5)4]2[2-SnCl(C6H5)2B10H9] (monoclinic space group P 21/c with a=17.263(2), b = 13 .045(3), c=26.171(2) Å, β = 102.882(7)°) reveals that the SnCl(C6H5)2 substituent is bonded with a B2-Sn distance of 2.168(4) Å.
Die Zwillings-Kristallstruktur von Mg(BrO3)2 · 6H2O / The Crystal Structure of Twinned Mg(BrO3)2 · 6H2O
Authors: Peter Stefan , Suchanek Ellen , Eßer Dirk , Lutz Heinz Dieter
Published: February 2015

The crystal structure of Mg(BrO3)2·6H2O twinned crystals has been determined by X-ray single crystal diffraction (Pa3̅, a = 1039.56(9) pm). The structure is isomorphic to that of M(BrO3)2·6H2O(M = Co, Ni, Cu, Zn) and Ni(ClO3)2·6H2O. The Mg(BrO3)2·6H2O structure is related to fluorite, with Mg(H2O)6
2+ replacing Ca2+ and BrO3
- replacing F-. The water molecules are involved in nearly linear hydrogen bonds to adjacent bromate ions (νOD of matrix isolated HDO: 2458 and 2453 cm-1). The intramolecular O-H distances 96.84 and 96.90 pm have been derived from the wavenumbers of the respective OD stretches using a recently established vOD vs. rOH correlation curve. The infrared and Raman spectra show accidental degeneracy of the symmetric and the asymmetric BrO stretching modes, which is common for bromate ions with local C3v symmetry.
Intramolekular verbrückte Organo-bis[dialkylaminochlorborane] / Intramolecularly Bridged Organo-bis[dialkylaminochloroboranes]
Authors: Wienmann Wolfgang , Hergel Achim , Deforth Thomas , Krämer Albrecht , Pritzkow Hans , Siebert Walter
Published: February 2015

The synthesis and structural properties of organo-bis-dialkylaminochlorboranes X(BNR2Cl)2, X = R2NB(CHCH3)2, o-C6H4, 1-α-C6H4CH2, and 1.8-C10H6 are reported. The steric influence of the alkylamino group and the geometrical situation caused by a chain of sp2 or sp3 hybridized carbon atoms control the formation of intramolecular donor-acceptor bonds. In o-(C6H4)(BNMe2Cl)2 (5) only one amino-boron donor-acceptor bond is observed. The steric influence of the alkyl groups in R2NB(CHCH3BClNR2)2 is discernible from the formation of two donor-acceptor bonds in 7a (R = Me), whereas 7b (R = iPr) is a non-bridged species. The reaction of benzomagnesacyclobutene with chlorbis(dimethylamino)borane yields cyclic 1-α(C6H4CH2)(BNMe2Cl)2 (9). 1,8-Dilithionaphthalene reacts with ClB(NR2)2 (R = Me, Et, iPr) to yield 1,8-(C10H6)[B(NR2)2]2 (10a-c), its reaction with BCl3 gives 1,8-(C10H6)(BClNR2)2 (11a: R = Me; 11b: R = Et; 11c: R = iPr). In 11a,b two tetracoordinate boron atoms are observed, in 11c the steric hinderance of the isopropyl substituents prevents donor-acceptor bonding.
Synthese, Schwingungs- und Massenspektren von Et2Sn(O2PR2)2 (R = Me, Ph); Kristallstruktur von Et2Sn(O2PPh2)2 / Synthesis, Vibrational Spectra and Mass Spectra of Et2Sn(O2PR2)2 (R = Me, Ph); Crystal Structure of Et2Sn(O2PPh2)2
Authors: Shihada Abdel-Fattah , Weller Frank
Published: February 2015

Et2Sn(O2PPh2)2 has been synthesized by the reaction of (Et2ClSn)2O with Ph2POCl in toluene and by the treatment of (Et2ClSn)2O or Et2SnCl2 with HO2PPh2 in methanol. The reaction of Et2SnO with HO2PMe2 in toluene was used to prepare Et2Sn(O2PMe2)2. An X-ray diffraction study of Et2Sn(O2PPh2)2 (space group P1̅, Z = 1, a = 559,9( 1), b = 983,7(1), c = 1262,4(l)pm, α = 81,85( 1 )°, β = 79,79( 1)°, γ = 75,00(1)°; structure refinement with 2662 independent reflections, R = 0.055) shows that the structure is polymeric and the O2PPh2 ligands function as double bridges between the tin atoms leading to the formation of centrosymmetric Sn2O4P2 eight-membered rings. The ethyl groups are in trans-position in the resulting octahedral environment around tin. The I. R. and Raman spectra of Et2Sn(O2PR2)2 (R = Ph, Me) have been discussed and assigned. The mass spectra of Et2Sn(O2PR2)2 show Sn(O2PR2)+ as the base peak.
Structure and Magnetic Properties of a Triply Oxygen. Bridged Dinuclear Ni(II) Complex
Authors: Elerman Yalcin , Kabak Mehmet , Svoboda Ingrid , Fuess Hartmut , Griesar Klaus , Haase Wolfgang
Published: February 2015

[Methylamino-(N,N′-1,3-propyl-disalicylaldiminato)-Ni(II)-bis-(N-methylsalicylaldiminato)- Ni(II)] was synthesized from the condensation of N,N′-1,3-propyl-disalicylaldimine, salicylaldehyde, methylaminohydrochloride, NaOH and Ni(CH3COO)2·H2O, and its crystal structure determined. [C34H37N5O4Ni2], orthorhombic, space group Pbca, a = 12.330( 1), b = 24.967(2), c = 20.616(2)Å, Z = 8. The dinuclear complex contains two octahedrally coordinated nickel atoms which are linked via three oxygen atoms with an average (Ni-O-Ni) angle of 87.2( 1)° and a Ni···Ni distance of 2.884(1)Å. The coordination is completed by three nitrogen atoms. The nickel(II) centers are ferromagnetically coupled (J = 11.5 cm-1) as derived from temperature-dependent magnetic susceptibility measurements in the range 5 - 280 K.
Synthese, Koordinationschemie und Ligandeneigenschaften sekundärer Phosphane R(Ar*)PH mit sperrigen aromatischen Resten - Molekülstruktur von Ph(2,4,6-iPr3C6H2)PH, (2,4,6-iPr3C6H2)2PH und ClAu[PhP(2,4,6-Bu3C6H2)H] / Synthesis, Coordination Chemistry and Ligand Properties of Secondary Phosphines R(Ar*)PH with Bulky Aromatic Substituents - Molecular Structure of Ph(2,4,6-iPr3C6H2)PH, (2,4,6-iPr3C6H2)2PH and ClAu[PhP(2,4,6-tBu3C6H2)H]
Authors: Brauer David J. , Bitterer Frank , Dörrenbach Frank , Heßler Gisbert , Stelzer Othmar , Krüger Carl , Lutz Frank
Published: February 2015

The secondary phosphines R(Ar*)PH(R = Me, iPr, Ph, Mes, Ar*) (2a-2h) with bulky aromatic substituents Ar* (Ar* = 2,3,6-R′ 3C6H2, R′ = iPr, tBu) are obtained in good yields by reaction of RPCl2, PCl3, PBr3 or Ar*P(Cl, Br)2 with 2,4,6-tBu3C6H2Li or 2,4,6- iPr3C6H2MgBr and subsequent reduction of the intermediate halophosphines R(Ar*)PX(X = Cl, Br) with LiAlH4. The X-ray structural analysis of Ph(2,4,6-iPr3C6H2)PH (2g), space group P1, shows P-C-distances of 1.824(1) and 1.838(1)Å. The lithium derivatives of 2a-2c are monomeric in solution as indicated by the 1 :1 :1 : 1-quartet 7L i - 31P fine structure of the 31P {1H} NMR signals at low temperatures. 2a-2c and 2f-2h form Ni(0) and Fe(0) complexes (CO)3NiL (6a-6f) and Fe(CO)4L (7a-7d), respectively. The Tolman electronic parameters of the bulky ligands are almost identical. Within the series 2a-2h the spatial shielding of the P atoms has been estimated using advanced molecular modeling techniques. The bulky ligand 2c forms coinage metal complexes [C u(CH3CN)2(2c)2] [PF6] (8), Cu2Cl2(2c)2 (9) and Cl-Au(2c) (10). While 10 is monomeric in solution, in the solid state it forms pairs of head to tail oriented monomers with almost linear Cl - Au - P skeletons (Cl - Au - P 175.47(9)°) as shown by an X-ray structural analysis.
Elektronentransfer und Ionenpaar-Bildung, 47 [1] Titrationen von 1,2,4,5-Tetracyanbenzol und 7,7,8,8-Tetracyan-p-chinodimethan mit Natriummetall in aprotischen Lösungen / Electron Transfer and Ion Pair Formation, 47 [ 1 ] Titrations of 1,2,4,5-Tetracyanobenzene and 7,7,8,8-Tetracyano-p-quinodimethane with Sodium Metal in Aprotic Solutions
Authors: Bock Hans , Kleine Markus
Published: February 2015

In an especially designed and sealed glass apparatus, a combination of UV/VIS and ESR spectroscopy measurements are performed to follow electron transfer reactions in aprotic (cH⊕ < 0,1 ppm) solution. For the sodium metal reductions of the tetracyano-substituted title compounds, the novel technique provides the following detailed information: 1,2,4,5- tetracyanobenzene is uniformly reduced to its radical anion, for which additional geometryoptimized MNDO calculations predict an already significant cyanine disortion. For 7,7,8,8- tetracyano-p-quinodimethane, UV/VIS band shape analysis allows to detect in the saturated THF reduction solution the 16300 cm-1 absorption of the donor/acceptor complex formed in the equilibrium TCNQ·⊖ + TCNQ ⇆ {TCNQ·⊖···TCNQ}, which according to a literature search has been crystallized and structurally characterized in paramagnetic salts such as [Me2
⊕ (TCNQ·⊖)2(TCNQ)].