bluuebunny/crossref_metadata_2025 huggingface dataset:
Komplexe mit substituierten 2,5-Dihydroxy-p-benzochinonen: Die Schichtverbindung Ca[C6(i-C3H7)2O4H]2·2/3H2O / Complexes with Substituted 2,5-Dihydroxy-p-benzoquinones: The Layer Compound Ca[C6(i-C3H7)2O4H]2·2/3H2O
Authors: Robl Christian , Sheldrick George M.
Published: March 2015

Dark, hydrophobic single crystals of Ca[C6(i-C3H7)2O4H]2·2/3H2O were grown in aqueous silica gel. Infinite layers parallel to (001) formed by Ca2+ and [C6(i-C3H7)2O4H]- are the main feature of the crystal structure. Ca2+ is coordinated in two different manners. Ca(1) has CN7: the coordination polyhedron is a slightly distorted capped trigonal antiprism made up by one water molecule and six oxygen atoms (O(1), O(2)) of the anions which chelate Ca(1). The mean Ca(1)-O distance is 238.9 pm. The coordination polyhedron of Ca(2) is a distorted octahedron formed by six anions acting as monodentate ligands via O(3): Ca(2)-O(3) 227.3 pm. In one half of the [C6(/-C3H7)204H] anion the bonding geometry resembles that of the corresponding dianions, but in the other half the bond lengths are very similar to those observed in free 2,5-dihydroxy-p-benzoquinones. The remaining H atom of the anion is involved in strong intramolecular hydrogen bonding as well as in an intermolecular hydrogen bond.
Synthesis of Quaternary Salts from 3,3′ -Bipyridine and Dibromoalkanes
Authors: Singh Shyam K. , Summers Lindsay A. , Hick Larry A.
Published: March 2015

Reaction of 3,3'-bipyridine with 1,3-dibromopropane, 1,4-dibromobutane, 1.5-dibromo-pentane, 1,6-dibromohexane. 1,7-dibromoheptane and 1.8-dibromooctane affords the corresponding bridged diquaternary salts, the structures of which were confirmed by fast atom bombardment mass spectrometry. Reaction with 1,2-bromoethane gives instead 1.1"-(1,2-ethanediyl)-bis-3.3'-bipyridinium dibromide.
Dianion eines Methylendiborirans, Synthese seiner Alkali- und Magnesiumsalze und Struktur seines Dikaliumsalzes / Dianion of a Methylenediborirane, Synthesis of its Alkali and Magnesium Salts and Structure of its Dipotassium Salt
Authors: Meyer Harald , Schmidt-Lukasch Günter , Baum Gerhard , Massa Werner , Berndt Armin
Published: March 2015

Lithium, sodium, potassium, caesium and magnesium salts of the dianion of 1,2-di-tert-butyl-3- [bis(trimethylsilyl)methylene]-1,2-diborirane have been synthesized and charactarized by 13C and 11B NMR spectroscopy. X-ray structure analysis of the di-potassium salt proves cyclic derealization of two. π-electrons in the CB2-ring by short C-B (150 pm) and B -B (158 pm) bonds. The exocyclic C-C bond (150 pm) is bridged by two potassium ions. One of them contacts the boron atoms of a neighbouring dianion leading to a helicoidal infinite chain with 41-symmetry along the c direction.
Untersuchungen zur Bildung von Flüssigkristallen bei Distyrylbenzolen mit Alkoxyketten / Investigations on the Formation of Liquid Crystals by Distyrylbenzenes with Alkoxy Chains
Authors: Meier Herbert , Praß Ellen , Zerban Georg , Kosteyn Frank
Published: March 2015

The syntheses of 1.2-, 1.3- and 1,4-distyrylbenzenes with four or six dodecyloxy chains (1→5a, b, c, 6→13). and the structural conditions for the generation of liquid crystalline states are discussed. 5c forms a thermotropic smectic phase, which is degradated by light and renewed in the dark.
Synthesis of 2-Acetoacetyl- and 2-OxaIoacetyl-1,3-indandiones and Related Compounds
Authors: Hamama W. S. , Hammouda M. , Afsah E. M.
Published: March 2015

Claisen condensation of 2-acetyl-1,3-indandione (1) with ethyl acetate afforded the 2-acetoacetyl-1,3-indandione (2) which upon treatment with benzylamine and paraformaldehyde in a molar ratio of (1:1:2) and (1:2:4) afforded the piperidinone and the diazabicyclic derivative (4) and (5) respectively. On the other hand, Claisen condensation of 1 with diethyl oxalate yielded two products (6) and (9). The behaviour of 6 towards phenyl hydrazine, and of 9 towards selenium dioxide and double Mannich reaction were also investigated.
Synthesis and X-Ray Analysis of the (S) Enantiomer of Methyl 5-Hydroxy-3,11-di-2-pyridyl-4,5-dihydro-1H,3H-2,6-methano- 6-benz[c]azocinecarboxylate C24H23N3O3 and of the Corresponding Camphanic Acid Ester C34H35N3O6
Authors: Hesse K.-F. , Holzgrabe Ulrike , Piening Barthold
Published: March 2015

Methyl 5-hydroxy-3,11-di-2-pyridyl-4,5-dihydro-1H,3H-2,6-methano-6-benz[c]azocinecarb-oxylate (-)-3 is synthesized by oxidative cyclization of an N-benzyl-4-piperidone, reduction and resolution with (-)-camphanic acid chloride.

The structures of C24H23N3O3 (-)-3 and of the corresponding camphanic acid ester C34H35N3O6 (-)-5 are orthorhombic and monoclinic with space groups P212121 ((-)-3) and P21 ((-)-5). The respective cell parameters are a = 9.758(3), b = 12.815(2), c = 16.584(4) Å, Z = 4 and Dx = 1.29 g cm-3 ((-)-3) and a = 11.189(1), b = 10.591(1), c -12.84(1) Å, β = 92.53(1)°, Z = 2, Dx = 1.27 g cm-3 ((-)-5). They were refined to R (unweighed) -0.037 ((-)-3), 0.069 ((-)-5) and R (weighed) = 0.035 ((-)-3), 0.061 ((-)-5) using 965, 1722 non-equivalent reflections, respectively. The absolute configuration of (-)-3 was determined as 2S, 3R. 5R, 6R, 11 R.
Durch Trichloracetat ausgelöste Alkylierungen von Trichlormethylketonen und eine komplexe Folgereaktion [1] / Alkylations of Trichloromethylketones Effected by Trichloroacetate and a Complex Consecutive Reaction [1]
Authors: Dehmlow Eckehard V. , Raths Hans-Christian
Published: March 2015

A phase transfer reaction between the title ketones, sodium trichloroacetate, and an alkyl halide leads to 2a, b, 4, or 5. Whereas these com-pounds are fragmented by NaOH, sodium meth-oxide/methylmalonate/methanol give compound 8 from 5 in a complex series of consecutive rearrange-ments.
Vergleich der NMR-Parameter von Phosphaalkinen und Nitrilen / Comparison of NMR Parameters of Phosphaalkynes and Nitriles
Authors: Wrackmeyer Bernd
Published: March 2015

The values 1J(15N≡13C) from 15N satellites in the 13C NMR spectra for two nitriles [C6H5-C≡N, (CH3)2CH-C≡N] have been determined and δ(15N) for trimethylsilylcyanide has been con- firmed. This completed a set of NMR parameters in order to compare phosphaalkynes and nitriles. Linear relationships emerged for the following NMR parameters of phosphaalkynes and nitriles: δ(31Pp≡c)/δ(15NN≡C), δ(13CP≡C)/δ(13CN≡C) and 1J(31P=13C)/1J(15N≡13C). On the basis of the latter relationship a positive sign for 1J(31P≡13C) has been proposed. This is also corroborated by the sub- stituent-induced changes in the magnitude of 1J(13C≡13C) in corresponding alkynes.
Über die Reaktion von Dicyan mit Cd(II)-Ionen Röntgenstrukturanalyse von [Cd{(CN)2}2SO2 ][AsF6]2/ The Reaction of Cyanogen with Cd(II) Ions X-Ray Structure Analysis of [Cd{(CN)2}2SO2][AsF6]2
Authors: Roesky Herbert W. , Schimkowiak Jürgen , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

Cd[AsF6]2 (1) reacts with cyanogen to yield [Cd{(CN)2}2SO2][AsF6]2 (2). 2 crystallizes in the space group Pnma with cell constants a = 1475.2(3); b = 821.7(3); c = 1321.2(9) pm. The coordination sphere of cadmium consists of nine atoms (one oxygen, four fluorines and four nitrogens). Cyanogen forms polymeric links.
Aluminiumbromid-Pyridiniumbromid-Verbindung: Kristallstruktur Kristallstrukturbestimmung von [Tris(pyridinium)bromid]bis(tetrabromoaluminat(III))/ Aluminiumbromide-Pyridiniumbromide Compounds: Crystal Structure Crystal Structure Determination of [Tris(pyridinium)bromide]bis(tetrabromoaluminate(III))
Authors: Burger Harald , Hensen Karl , Pickel Peter
Published: March 2015

The compound [(PyH)3Br][AlBr4]2 is formed by melting stoichiometric amounts of AlBr/PyHBr in a ratio of 2:3. It crystallizes in the orthorhombic space group Pbca with lattice constants a = 1365.5(2), b = 1616.0(2), c = 2783.7(3) pm, Z = 8, Dc = 2.21 g/cm3. The structure was solved from 2810 diffractometer measured intensities (Cu -Kα radiation) and refined to Rw (F) = 0.071. The cation shows three pyridinium ions attached via N - H - Br hydrogen bonds to a central bromide ion. The N - Br distances are 321(1), 321(2) and 332(2) pm.
Unsymmetrisch substituierte Phosphinoschwefeldiimide – NMR-Untersuchungen über die Konfiguration in Lösung/ Unsymmetrically Substituted Phosphino Sulfur Diimides – NMR Studies on the Configuration in Solution
Authors: Herberhold Max , Frank Stefan M. , Wrackmeyer Bernd
Published: March 2015

The phosphino-substituted sulfur diimides S(N-PtBu2)2 (1), tBu;P(NSN)PRR′ (R = R′ - phenyl (2a), cyclohexyl (2b), isopropyl (2c), ethyl (2d); R = phenyl, R′ = tert-butyl (2e)) and tBu2P(NSN)tBu (3) were studied in solution by 1H, 13C and 31P NMR spectroscopy**. The coupling constants 4J(31P31P) of the compounds containing different phosphino groups, 2a-e, depend both on the nature of the solvent and the temperature. The NMR results are interpreted in accord with a rapid Z/E⇄ E/Z interconversion at room temperature and the predominance of a single configurational isomer at low temperatures. There is no indication for the presence of the “symmetrical” configurations, Z/Z or E/E respectively, in solution in appreciable amounts. 15N NMR data are also reported for a series of sulfur diimides.
Darstellung von Dichalkogenostibanen des Typs RSb(ER′)2 (R = CH3, C2H5; E = S, Se; R = CH3, C6H5)/ Preparation of Dichalcogenostibanes of the Type RSb(ER′)2 (R = CH3, C2H5; E = S, Se; R′ = CH3, C6H5 )
Authors: Breunig Hans Joachim , Güleç Sabahittin
Published: March 2015

Dichalcogenostibanes of the type RSb(ER′)2 (R = CH3 ,C2H5; E = S. Se; R′ = CH3. C6H5) and trialkylstibanes R3Sb have been prepared by redistribution reactions of stibanes of the type R2SbER′.
Synthese und Eigenschaften von tert-Butyltriiodsilan/ Synthesis and Properties of tert-Butyltriiodosilane
Authors: Baudler Marianne , Arndt Uwe , Grenz Detlef
Published: March 2015

tert-Butyltriiodosilane (1) has been prepared in its pure form by heating tert-butylsilane (2) with iodine. Compound 1 has been characterized by elemental analysis as well as by spectroscopic methods.
Synthesis and Activity of Juvenile Hormone Analogues (JHA)
Authors: Rodriguez Juan B. , Gros Eduardo G. , Stoka Angel M.
Published: March 2015

From geranylacetone and by the use of a variety of reagents, twelve analogues of the juvenile hormone III were synthesized. The compounds (5-16) have an isoprenic structure bearing at the extreme of the chain functional groups as carbonate, carbamate, thiolcarbonate, thiolcarbamate, carbonyloxyimino and thiol carbonyloxyimino. Compounds 5-9 present the normal unsaturated isoprenic chain while compounds 10-16 have a monoepoxide function. All the compounds were tested for their respective juvenile hormone activity for Triatoma infestans and Rhodniusprolixus. The most active compounds were those having a thiol carbonate group independently of the oxidation state of the molecule. The synthetic procedures and the biological results are discussed.
The Crystal Structure of Potassium Nickel Arsenate; KNiAsO4
Authors: Buckley A. M. , Bramwell S. T. , Day P. , Harrison W. T. A.
Published: March 2015

The crystal structure of potassium nickel arsenate. KNiAsO4 has been determined by high resolution powder neutron diffraction at 30 K. The unit cell of KNiAsO4 is rhombohedral. space group R3̄, with hexagonal cell constants, a = 4.97208(2) (Å). c = 28.52606(10) (Å). The compound is isomorphous with NaNiAsO4.
Elektronenreiche Olefine, 2 Struktur und Elektrontransfer-Reaktivität des cyclisch σ/π-hyperkonjugierten Carbosilans 3,3,6,6-Tetrakis(trimethylsilyl)-1,4-cyclohexadien
Authors: Hausen Hans-Dieter , Bessenbacher Christian , Kaim Wolfgang
Published: March 2015

Crystal and molecular structure analysis of the title compound 1, a most electron rich carbosilane, exhibits a shallow boat conformation for the cyclohexadiene ring which is shielded by four bulky Me3Si groups. Multiple hyperconjugative interaction occurs between the two non-conjugated olefinic π systems and the four rather long (192 pm) carbon-silicon o bonds which form an angle of about 34° with the assumed π axis. The HOMO destabilization caused by this unique structural arrangement explains the energetically facile formation and subsequent reactivity of the cation radical 1+ which was found to undergo oxidative desilylation to the aromatic 1,4-bis(trimethylsilyl) benzene precursor in the single electron transfer reaction with TCNE.
Tetrakis[bis(trimethylsilyl)methyl]dialan(4), eine Verbindung mit Aluminium—Aluminium-Bindung
Authors: Uhl Werner
Published: March 2015

The reaction of chloro-bis[bis(trimethylsilyl)methyl]alane (1) with potassium yields the title compound 2.2 crystallizes in the triclinic space group P1̄ and shows an aluminium -aluminium bond length of 266.0(1) pm. The core of the molecule is almost planar.
Die Kristallstruktur von N,N,N'-tris(trimethylsilyl)benzamidin sowie die Synthese und Kristallstruktur von DichIorantimon-N,N'-bis(trimethylsilyl)benzamidinat
Authors: Ergezinger Christina , Weller Frank , Dehnicke Kurt
Published: March 2015

N,N,N'-Tris(trimethylsilyl)benzamidine, [C6H5-C(NSiMe3)N(SiMe3)2], reacts with antimony trichloride in CH2Cl2 solution to form monomeric dichloroantimony-N,N'-bis(trimethylsilyl)- benzamidine, [SbCl2(NSiMe3)2C-C6H5]. Both benzamidine derivatives have been character­ized by crystal structure determinations. [C6H5-C(NSiMe3)N(SiMe3)2]: space group P21/c, Z = 4, 2278 observed independent refle­xions, R = 0,038. Lattice dimensions (19 °C): a = 1521,0(1); b = 656.7(1); c = 2163,0(1) β = 94,21(1)°. The compound forms monomeric molecules with CN distances of 126,6 pm, and 141,0 pm, respectively, corresponding to C=N̄-SiMe3 and C-N(SiMe3)2 moieties. [SbCl2(NSiMe3)2C-C6H5]: space group P21/c, Z = 4, 2707 observed independent reflexions, R = 0,027. Lattice dimensions (19 °C): a = 1212,7(1); b = 962,1(1); c = 1728,9(1) pm; β = 98,02(1)°. The compound forms monomeric molecules in which the antimony atom is surrounded by two chlorine atoms, and by the N atoms of the benzamidine chelate, forming a distorted trigonal bipyramidal arrangement, which is a consequence of the steric effect of the lone pair on the Sb atom.
The Reactions of Hydroxyl Radicals with 1,4-and 1,3-Cyclohexadiene in Aqueous Solution
Authors: Pan Xian-Ming , Bastian Eugenie , Sonntag Clemens von
Published: March 2015

The reactions of radiolytically generated hydroxyl radicals and H atoms with 1,4- and 1,3-cyclohexadiene were studied by pulse radiolysis and product analysis. Hydrogen abstraction from these substrates by the OH radical yields the cyclohexadienyl radical (ε (310 nm) = 4400 dm3 mol-1 cm-1 from the reaction of the H atom with benzene) with an efficiency of 50% (0.29 ,μmol J-1) in the case of 1,4-cyclohexadiene and 25% (0.15 ,μmol J-1) in the case of 1,3-cyclohexadiene as determined by pulse radiolysis. The remaining OH radicals add to the olefin. In 1.4-cyclohexa- diene the yield of the resulting adduct radicals has been determined in a steady-state 60Co-γ-irradiation experiment by reducing it with added 1.4-dithiothreitol (DTT) to 4-hydroxycyc- lohexene. There are two sites of OH radical attack in the case of 1.3-cyclohexadiene, and only the alkyl radical is reduced quantitatively by DTT (G(3-hydroxycyclohexene) = 0.15 ,μmol J-1). From material balance considerations it is concluded that the allylic radical must be formed with a G value of 0.28 ,μmol J-1 but largelv escapes reduction by DTT (G(4-hvdroxycyclohexene) = 0.03 ,μmol J-1). H atoms add preferentially to the double bonds of 1,4- and 1,3-cyclohexadiene (78% and 93%, respectively), while the O.- radical (the basic form of the OH radical) undergoes mainly H- abstraction (92% and 83%, respectively). The radicals formed in these systems decay bimolecularly (2k = 2.8 x 109 dm3 mol-1 s-1). In their combination reactions the cyclohexadienyl radicals form the four possible dimers in propor­tions such that the dienyl radical moiety shows a 2:1 preference to react from its central (1a) rather than from a terminal carbon atom (1b). Cyclohexadienyl radicals and the OH- and H-adduct radicals also cross-tcrminate by disproportionation and dimerization. Material balance has been obtained for the 1,4-cyclohexadiene system in N2O-Saturated solution (10-2 mol dm-3) at a dose rate of 0.14 Gy s-1, the products (G values in ,μmol J-1) being: benzene (0.085), 4-hydroxycyclohexene (0.25), cyclohexadienyl-dimers (0.144). cvclohexadienyl-OH-adduct- dimers (0.02), OH-adduct-dimers (0.02). Some of the 4-hydroxycyclohcxene is formed in an H-abstraction reaction by the OH-adduct radical from 1,4-cyclohexadiene.
Darstellung und Kristallstruktur von Ca5Ga2N4 / Preparation and Crystal Structure of Ca5Ga2N4
Authors: Cordier Gerhard
Published: March 2015

The crystal structure of Ca5Ga2N4 (orthorhombic, space group Cmca, a = 487.3(2) pm, b =1110.5(3) pm, c = 1421.7(4) pm, Z = 4) contains infinite zig-zag chains of Ga atoms, which are in a tetrahedral coordination by two additional nitrogen atoms in terminal positions.
Neuer Syntheseweg und Molekülstruktur von (1,2,3-Triphenyltriphosphan-1,3-diyl)zirkonocen(IV), / A New Synthesis and the Molecular Structure of (1,2,3-Triphenyltriphosphane-1,3-diyl)zirconocene(IV),
Authors: Hey Evamarie
Published: March 2015

Cp2ZrCl2 reacts with an excess of PH2Ph in the presence of magnesium turnings to yield

(Cp = η5-C5H5) (1). Only the meso form of 1 is present in solution as well as in the solid state [with R or S configuration of P(1), S or R of P(3)]. 1 crystallizes monoclinicly in the space group P21/c (Nr. 14) with Z = 4, a = 10.699(3), b = 15.065(3), c = 16.135(13) Å, β = 109.53(5)°. The structure was refined to R = 0.066 for 2082 reflections. The coordination of the P3Ph3
2- ligand to the Cp2Zr fragment is nearly symmetrical (Zr-P: 2.635(2) and 2.622(2) Å), and the ZrP3 metallacycle is almost planar.
Darstellung des Stibinoschwefeldiimid-Achtrings tBuSb(NSN)2SbtBu und einiger seiner Carbonylmetall-Derivate / Synthesis of the Eight-Membered Stibino-Sulfur Diimide Ring tBuSb(NSN)2SbtBu and Some of its Carbonylmetal Derivatives
Authors: Herberhold Max , Schamel Klaus
Published: March 2015

The first antimony-sulfur-nitrogen heterocycle, tBuSb(NSN)2SbtBu (1b)**, has been prepared from the reaction of tBuSbCl2 with the salt K2SN2. It forms stable chelate complexes of the type (CO)4M[tBuSb(NSN)2SbtBu] (M = Cr (3b), Mo (4b), W (5b)). The pentacarbonylchromium complex (CO)5Cr[tBuSbCl2] reacts with K2SN2 to give the mononuclear derivative (CO)5Cr[tBuSb(NSN)2SbtBu] (2b) containing the eight-membered ring 1b, whereas the corre-sponding complexes (CO)5Cr[R2SbCl] (R = tBu, Ph) are converted into binuclear sulfur diimide derivatives (CO)5Cr[R2Sb(NSN)SbR2]Cr(CO)5 (R = tBu (6b). Ph (7b)). The new stibino-sulfur diimides 1b-7b have been characterized by IR and NMR (1H and 13C) spectroscopy.
Hydratisierte Cyanoelpasolithe: Bis(tetramethylammonium)diaquaIithium-hexacyanometallate(III) des Mangans, Eisens und Cobalts / Hydrated Cyanoelpasolites: Bis(tetramethylammonium)diaqualithium-hexacyanometallates(III) of Manganese, Iron and Cobalt
Authors: Witzel M , Ziegler B , Babel D
Published: March 2015

The crystal structures of three isotypic hexacyanometallates(III) (NMe4)2LiM(CN)6·2H2O have been determined and refined in the monoclinic space group C2/c, Z = 4, to wR = 0.053 (M = Mn, 959 independent single crystal reflections), 0.041 (M =Fe, 2002 reflections) and 0.037 (M = Co, 1881 reflections). The stucture is elpasolite-related by its face-centered pseudocubic arrangement of M atoms within nearly undistorted M(CN)6
3- octahedra, six of which form strongly distorted octahedral N6 cavities occupied by dihydrated lithium ions. The resulting average distances for the M(CN)6
3- octahedra are Mn-C = 201, Fe-C = 194.7, Co-C = 190.3, and C-N = 114 pm. The lithium coordination is distorted tetrahedral, consisting of LiO2N2 units with distances of about Li-O = 194, Li -N = 209 pm (for M = Fe, Co). The remaining four N atoms of the N6 cavity are bound by hydrogen bridges from the two aqua ligands, O-H···N = 283 and 295 pm. The relations to the hydrated elpasolite structure of (NMe4)2NaFe(CN)6·H2O are discussed.
Biosynthesis of Riboflavin. A Simple Synthesis of the Substrate and Product of the Pyrimidine Deaminase and of Structural Analogs
Authors: Nielsen P , Bacher A
Published: March 2015

2-Amino-5-nitro-6-ribitylamino-4(3H)-pyrimidinone (7) was phosphorylated with chlorophosphoric acid yielding an isomer mixture containing about 63% of the 5´-phosphate 7a together with other monophosphates and bisphosphates of 7. Preparative HPLC afforded pure 7a. Catalytic hydrogenation of 7a yields the labile substrate of pyrimidine deaminase, 2,5-diamino-6-ribityl-amino-4(3H)-pyrimidinone 5´-phosphate (2a). The product of the enzyme, 5-amino-6-ribityl-amino-2,4(1H,3H)-pyrimidinedione 5´-phosphate (4a), can be obtained from 5-nitro-6-ribityl-amino-2,4(1H,3H)-pyrimidinedione (8) by an analogous procedure. The 3´-and 4´-monophos-phates of 2,5-diamino-6-ribitylamino-2,4(1H,3H)-pyrimidinedione are not substrates for the deaminase. 5´-Phosphates of a variety of ribityl-substituted pyrimidines and pteridines could also be obtained by phosphorylation with chlorophosphoric acid without the use of protecting groups.
Diolefinbis(trimethyIphosphine)cobalt(0) Compounds: Stable Organometallic Radicals with Distorted Ground State Structures
Authors: Klein Hans-Friedrich , Helwig Michael , Koch Udo , Lull Goetz , Tadic Marko , Krüger Carl , Hofmann Peter
Published: March 2015

Diolefincobalt(O) complexes Co(L2)(PMe3)2 {L2 -[CH2 = CHSi(OMe)2]2O (1), [CH2 =CHSi(OEt)2]2O (2), (CH2 =CHCH2)2SiMe2 (3), [(CH2 =CHCH2)2N]2CH2 (4)} have been synthesized from Co(C5H8)(PMe3)3 and diolefins at ambient temperatures. Reactions with allyl ethers or with allyltin or allylphosphorus compounds involve transfer of allyl groups to the cobalt, while allylamine simply replaces cyclopentene (C5H8) to give Co(CH2 =CHCH2NH2)(PMe3)3 (5). Cationic cobalt(I) complexes containing olefin ligands as in 1-4 could not be obtained under conditions where norbornadiene readily gave [Co(C7H8)(PMe3)3 ]BF4 (6). Paramagnetic 4 shows a magnetic moment μeff = 2.0 μв (between 3.6 and 293 K), corresponding to one unpaired electron per cobalt atom. Compound 4 crystallizes in the space group P21/c with Z = 4, a = 14.986(4), b = 17.223(5), c = 15.436(3) Å,β = 117.98(2)°, V = 3518.4 Å3 . Each cobalt atom is η4-coordinated to a diolefin involving the smaller of two possible chelating rings. The Co-C distances range only from 2.029(6) to 2.058(6) Å for the olefin ligands, whereas Co-P bond lengths at each cobalt differ significantly: Co1-P1 2.188(2), Co1-P2 2.248(2); Co2-P3 2.185(2), Co2-P4 2.258(2) Å. This feature of two significantly different Co-L bond lengths is hitherto seen in all structurally characterized (bisolefin)CoL2 complexes (L = PMe3, CH3CN) and can be rationalized by molecular orbital calculations (Extended Hückel) on the 17 electron model system (PH3)2Co(C2H4)2.
Strukturen und Schwingungsspektren neuer Wolframatophosphate / Structures and Vibrational Spectra of Novel Tungstophosphates
Authors: Fuchs Joachim , Palm Rosemarie
Published: March 2015

A solution of Na2WO4 • 2H2O and Na2HPO4 (3:1) was acidified with acetic and perchloric acid, respectively, and yielded mixtures of crystals. These were mechanically separated under a microscope according to the appearance of the crystals and the pure phases were subjected to vibrational (IR and Ra) and X-ray investigations. The compounds have the formulae Na20P6W18O79 ·nH2O (I) with n = 41,32 and 12, and Na12P4W14O58 · 42H2O (II), respectively. By carrying out secondary reactions one obtains two more phases of (II) with less water of crystallization (36 and 34 H2O) as well as a hydrolysis product of (I), the compound Na20P5W18O75(OH)3-42H2O (III). The structures of (I) (41-hydrate), (II) (36-hydrate) and (III) were discussed. Besides centrally bound phosphate groups their anions also contain peripherally bound phosphate groups. These compounds can now be identified by the characteristic features of their vibrational spectra
Isomere vierkernige Molybdän—Wolfram—Schwefelclusterdithiophosphinate / Isomeric Tetranuclear Molybdenum—Tungsten — Sulfurclusterdithiophosphinates
Authors: Deeg Axel , Keck Helmut , Kruse Andreas , Kuchen Wilhelm , Wunderlich Hartmut
Published: March 2015

A mixture of three isomeric clusters of composition Mo3WS4(Et2PS2)6 (3) is obtained by reacting equimolar quantities of Mo3S4(Et2PS2)4, W(CO)3(CH3CN)3 and [Et2P(S)]2S2 in toluene'. Some NMR-spectroscopic data and the magnetic properties of these isomers are reported. Isomer 3a consists of a distorted cubane Mo3WS4, each metal of which is coordinated by six S atoms: three of them belonging to the cubane, one to a bridging and two to a chelating ligand Et2PS2
-. The crystal structure of isomer 3b is reported. In 3b only three of the metals in the core are coordinated in this manner while the fourth is surrounded by three S of the cubane and three S of bridging ligands. 3b crystallizes in the orthorhombic space group Pbca, Z = 8. lattice parameters a = 2184,4(8), b = 2264,4(9). c = 2388.2(8) pm. The crystal structure was refined to R = 0.05 using 5398 observed reflections. By HPLC 3b can be separated into two isomers. 3b1 and 3b2, both differing in the type of metal. Mo or W. bonded to the three bridging ligands
Nd7,33Ta8O28CI6 — ein Zwischenprodukt des thermischen Abbaus von Nd2Ta2O7Cl2: Präparation, Struktur und magnetische Eigenschaften / Nd7,33Ta8O28Cl6 — an Intermediate Product of the Thermal Decomposition of Nd2Ta2O7Cl2: Preparation, Crystal Structure and Magnetic Properties
Authors: Schaffrath U. , Gruehn R.
Published: March 2015

Single crystals of the new oxochlorotantalate Nd7.33Ta8O28Cl6, could be obtained only by chemical transport reactions (T2 → T1; T2 - 1000 °C, T, = 900 °C) with mixtures of Cl2/TaCl5 as transport agent. NdTaO4 was chosen as the starting material. A direct preparative route to Nd7.33Ta8O28Cl6 from binary and ternary components, however, was not successful. Nd7.33Ta8O28Cl6 , crystallizes in the space group Cmmm with a = 10.3381(8) Å, b = 18.865(1) Å, c - 3.9152(3) A; Z = 1. The structure was refined to R - 4.42%, R w = 2.76%. Main building units are pairs of edge-sharing TaO6 -octahedra which are connected with threefold capped trigonal prisms around Nd. Especially remarkable is one Nd position with an occupation factor of 0.833. The relationship of this new structure type with Nd2Ta2O7Cl2 is considered. Furthermore, we have measured the magnetic susceptibilities of both Nd-compounds in a temperature range from 3,6 to 251,3 K. The results are compared with calculated data.
Achtfachkoordination von Cadmium(II) und sekundäre Metall—Ligand-Bindungen in [Cd(NO3)2(C12H22N6)] und [Cd(C12H22N6)2(BF4)2 / Eight-Coordination of Cadmium(II) and Secondary Metal —Ligand Bonds in [Cd(NO3) 2(C12H22N6)] and [Cd(C12H22N6) 2(BF4)2
Authors: Strasdeit Henry , Pohl Siegfried
Published: March 2015

[Cd(NO3)2(C12H22N6)] (1), [Cd(C12H22N6)2](BF4)2 (2), and [Cd(C12H22N6)2](ClO4)2 (3) are obtained from methanolic solutions by reaction of 2,5,8,10,13,16-Hexaazapentacyclo[ 8.6.1.125.0918.0l3,7]octadecane (C12H22N6) with Cd(NO3)2-4H2O, Cd(BF4)2, and Cd(ClO4)2 · 6H2O, respectively. 1 crystallizes in the monoclinic space group C2/c with a = 10.346(1), b =18.162(1), c - 10.462(1) Å, β = 112.95(1)°, and Z = 4. 2 is monoclinic, space group P21/n, a = 16.958(1), b = 10.653(1), c = 18.747(1) Å, β= 112,66(1)°, and Z = 4. The X-ray structures of 1 and 2 were refined to R(Rw) = 0.028 (0.029) and 0.060 (0.057), respectively. The compounds contain discrete [Cd(NO3)2(C12H22N6)] and [Cd(C12H22N6)2]2+ complexes, respectively. The Cd atoms are eight-coordinated with four primary and four longer, secondary metal -ligand bonds. In both complexes the hexaamine has an axially symmetrical configuration and acts as a tetradentate ligand. The N03 ligands are aniso-bidentate. Mean bond lengths are (Cd -N)prim 2.308(3), (Cd-N)sec 2.676(3), (Cd-0)prim 2.331(2), (Cd-0)sec 2.593(3) Å for 1, and (Cd-N)prim 2.374 (ligand 1), 2.438 (ligand 2), (Cd-N)sec 2.746 (ligand 1), 2.702 Å (ligand 2) for2. In water the neutral complex 1 dissociates and behaves as an 1:2 electrolyte. 13C and 113Cd NMR data and the conductivity of solutions of 2 or 3 in dimethyl sulfoxide indicate a fast but incomplete exchange of the ligands in [Cd(C12H22N6)2]2+ by solvent molecules
Rhodium(I)-Komplexe mit 2,5-Difurfurylpyrrol-Liganden / Rhodium(I) Complexes with 2,5-Difurfurylpyrrole Ligands
Authors: Lindner Ekkehard , Schneider Horst W. , Fawzi Riad , Englert Ulrich , Hiller Wolfgang
Published: March 2015

The 2.5-difurfurylpyrrole-O.N.O ligands 3a, b [R = CO2C2H5 (a). COCH, (b)] are obtained by reaction of the furanes l a , b with the 2,5-bis(chloromethyl)pyrrole 2 in the presence of SnCl4. Proton abstraction from 3a, b with NaH affords the sodium salts 4a-Na and 4b-Na. Exchange of the chlorine bridges in [μ-ClRh(Diol)]2 (5,5') (Diol = cyclooctadiene, norbornadiene) results in the formation of the 14-electron complexes (Diol)Rh(O.N.O) (6a,6'a). Addition of PPh3, yields the four-coordinated rhodium complexes (Diol)Rh(O.N.O)(PPh3) (7a,7'a). These compounds are also available in a reverse reaction sequence from 5,5', PPh3, and 4a-Na. The mononuclear rhodium complexes RhCl(Diol)(PPh3) (8,8') are isolated as intermediates. In 7a, 7'a the olefinic ligands are replaced by carbon monoxide to give the dicarbonyl rhodium complex (OC)2Rh(O.N.O)(PPh3) (9a) being detectable only in solution. The same result is achieved upon addition of CO to the compound (OC)Rh(O.N.O)(PPh,) (11a) which results bv the reaction of [μ-ClRh(CO)(PPh3)]2 (10) with 4a-Na. Oxidative addition of CH3I or H2 to 6a, 6 a, 7a, 7'a or 11a was not observed. 1H and 31P{1H} NMR investigations indicate that depending on the temperature the O.N.O ligand in the 14-electron rhodium complex 11a acts as tri- (11a-A), bi- (11a-B) and monodentate (IIa-C) ligands. respectively. 11a also reacts with PPh, to form the /ram-bis(phosphane)rhodium complex (PPh3)2Rh(CO)(O.N.O) (12a). 12a and the analogous complexes 12b and trans-(PMe3)2Rh(CO)(O,N.O) (14a) are obtained by action of ClRh(CO)L2 (13) (L = PPh3. PMe3) on 4a-Na and 4b-Na, respectively. The methylene bridges in the O.N.O ligand 3a are not oxidized, neither in the non-complexed (3a) nor in the complexed (12a) state. According to an X-ray structural analysis 14a crystallizes in the monoclinic space group P21/n with Z = 4. In 6a, 6'a, 7a, 7'a, 9a, 11a, 12a, b, and 14a the O.N.O ligand is always nitrogen bonded
N,N'-Bis(trimethylsilyl)benzamidinato-Koniplexe von Titan und Zirkon. Die Kristallstrukturen von [C6H5-C(NSiMe3)2MCl3]2; M = Ti, Zr / N,N'-Bis(trimethylsilyl)benzamidinato Complexes of Titanium and Zirconium. The Crystal Structures of [C6H5-C(NSiMe3)2MCl3 ]2 ; M = Ti, Zr
Authors: Fenske Dieter
Published: March 2015

The N,N'-bis(trimethylsilyl)benzamidinato complexes [C6H5 -C(NSiMe3)2MCl3]2(M = Ti. Zr) have been prepared by the reactions of N,N,N'-tris(trimethylsilyl)benzamidine

[C6H5-C(NSiMe3)N(SiMe3)2] with titanium tetrachloride, and zirconium tetrachloride, respec-tively. The compounds form moisture sensitive, dark red (Ti) and white (Zr) crystals, which were characterized by crystal structure determinations. [C6H5-C(NSiMe3)2TiCl3]2 : space group P21/rc. Z = 2, 4373 observed independent reflexions, R = 0.034. Lattice dimensions (-90 °C): a - 959.0(8); b = 1196.5(8); c = 1770.9(11) pm; β = 93.79(4)°. [C6H5-C(NSiMe3)2ZrCl3]2 : space group P21/n. Z = 2, 3160 observed independent reflexions, R = 0.031. Lattice dimensions (-90 °C): a = 971.6(7); b = 1222.2(9); c = 1792.9(10) pm; β = 93.51(5)°.

Both complexes crystallize isotypically, forming centrosymmetric dimeric molecules via chloro bridges with bond lengths of 242.0 and 253.8 pm (Ti), and of 253.7 and 264.9 pm (Zr). The metal atoms complete their distorted octahedral surroundings with two chlorine ligands and the nitrogen atoms of the chelating amidinato ligand. The N atoms of the amidinato group are in equatorial and axial positions. This accounts for the different metal-nitrogen bond lengths of 207 pm (ax) and 199 pm (eq) in the titanium compound and 219 pm (ax) and 214 pm (eq) in the zirconium complex.
N-Chloronitrenokomplexe des Wolframs: Synthesen und Kristallstrukturen von PPh3Me[Cl5W(NCl)] und (PPh4)3{[Cl5W(NCl)]2Cl} • CCl4 • 4CH3CN / N-Chloro-Nitrene Complexes of Tungsten: Syntheses and Crystal Structures of PPh3Me[Cl5W(NCl)] and (PPh4)3{[Cl5W(NCl)]2Cl} CCl4-4CH3CN
Authors: Gorge Astrid , Patt-Siebel Ute , Müller Ulrich , Dehnicke Kurt
Published: March 2015

Abstrct

The N-chloro-nitrene complexes PPh3Me[Cl5W(NCl)] and (PPh4)3{ [Cl5W(NCl)]2Cl} • CCl4 • 4CH3CN were prepared by the reaction of [CI4W(NCl)]2 with [PPh3Me]Ci in CH2Cl2 and with [PPh4]Cl in CH3CN. respectively, followed by precipitation with CCl4. Both compounds form red, moisture-sensitive crystals, which were characterized by IR spectroscopy as well as by X-ray structure determinations. PPh3Me[CUW(NCl)]: space group P1̄, Z = 2, a = 862.7(3), b = 1108.4(2), c = 1411.0(5) pm. a = 71.74(3)°, β = 76.78(3)°, y = 77.55(2)° (at 18 °C); 2843 unique observed reflexions, R = 0.042. The compound consists of ions PPh3Me+ and [Cl5W(NCl)]-, in which the tungsten atom has a distorted octahedral environment of five chlorine atoms and the nitrogen atom of the N-chloro-nitrene ligand

with bond distances WN = 169 pm and N-Cl = 160 pm. bond angle WNCl = 175°.

(PPh4)3{[Cl5W(NCl)]2Cl} • CCl4• 4CH3CN: space group P4/n, Z = 2, a = 1298.2(8). c = 2720.4(7) pm (at 17 °C); (1979 unique observed reflexions. R = 0.096). The compound contains cations PPh4
+ and anions {[CI5W(NCl)]2Cl}3-, in which two [Cl5W(NCl)]- ions are bridged by a chloride ion to form the linear unit [Cl5W≡N-Cl ··· Cl -Cl-N≡WCl5]3- with Cl ··· Cl-contactsof 288 and 278 pm
Die Amino- und Azidoborierung von Iminoboranen / The Amino- and Azidoboration of Iminoboranes
Authors: Paetzold Peter , Meier Hans-Ulrich , Schwan Heinrich , Plotho Christoph von
Published: March 2015

Iminoboranes RB=NR" (3a-c; R/R" = iPr/iPr, Bu/tBu, iBu/iBu) are aminoborated by aminoboranes AO(A)N = BR'2 (1a - c ; R' = Et, Bu, 1/2 - CH2-CHMe -CH2-CH2-) or azidoborated by azidoboranes N3=BR'2 (2a-c; R' = Pr. Bu. Ph) to give products

(4a-d) or

(5a-d), respectively. Hypothetical alkyloboration of 3 by 1, 2 can be excluded by applying AO(A)N = 10BBu2 and N3=10BBu2 as boration agents (A = Me3Si)
Die Reaktion von N,N,N'-Tris(trimethylsilyI)benzamidin mit Kupfer(II)chlorid. Kristallstruktur von {C6H5-C(NSiMe3)2CuCl[C6H5-C(NSiMe3)(NHSiMe3)]}/ The Reaction of N,N,N'-Tris(trimethylsilyl)benzamidine with Copper(II) Chloride. Crystal Structure of {C6H5—C(NSiMe3)->CuCl · [C6H5-C(NSiMe3)(NHSiMe3)]}
Authors: Hey Evamarie , Ergezinger Christina , Dehnicke Kurt
Published: March 2015

,N,N'-Tris(trimethylsilyI)benzamidin mit Kupfer(II)chlorid. Kristallstruktur von {C 6 H 5 -C(NSiMe 3) 2 CuCl [C 6 H 5 -C(NSiMe 3)(NHSiMe 3)]} The Reaction of N,N,N'-Tris(trimethylsilyl)benzamidine with Copper(II) Chloride. Crystal Structure of {C 6 H 5 —C(NSiMe 3)->CuCl • [C 6 H 5 -C(NSiMe 3)(NHSiMe 3)]}
Synthesis and Crystal and Molecular Structure of trans-Dichloro(ethanedial dioximato(1—)-N,N')(ethanedial dioxime-N,N')rhodium(III)
Authors: Mégnamisi-Bélombé Michel
Published: March 2015

trans-Dichloro(ethanedial-dioximato)(ethanediaI-dioxime)rhodium (III), RhCl2(GH)(GH2), has been synthesized and its structure determined by single crystal X-ray diffraction at room temperature. C4H7Cl2N4O4Rh, Mr = 348.94. monoclinic space group P21/ɑ; a = 10.543(3), b = 8.363(2), c = 11.512(3)Å ; β = 92.79(2)°; V = 1024Å3; Z = 4; Dc = 2.26 Mg m-3. Final Rw = 0.075 for 2035 reflections and 139 parameters. The coordination geometry around Rh is a dis­torted (4+2) octahedron, with four chelating N atoms lying in the equatorial plane and the two Cl atoms in the apical positions. The H atoms of the oxime groups are involved in relatively weak intramolecular O-H-O bridgings, as well as in very strong intermolecular bridgings which extend throughout the crystal structure and propagate nearly parallel to the [101] crystallographic direction.
Neue Übergangsmetallkomplexe mit dem Liganden Me2S(O )=NPPh2=N— /New Transition Metal Complexes with the Ligand Me2S(O)=NPPh2=N —
Authors: Roesky Herbert W. , Schrumpf Frank , Noltemeyer Mathias
Published: March 2015

Abstract S,S-Dimethylsulfoximinato-diphenyl-N-trimethylsilylphosphoranylidenamin (1) reacts in a molar ratio of 1:1 with TiCl4, CpTiCl3, (Cp = C5H5), VOCl3, and Cp*TaCl4 (Cp* = C5Me5) to yield the 1:1 adduct 1 · TiCl4 (2) and the substituted products Me2S(O) = NPPh2 = N-TiCpCl2 (3), Me2S(O) = NPPh2=N-VOCl2 (4) and Me2S(O) = NPPh2 = N-TaCp*Cl3 (5). The structures of 3, 4 and 5 show short metal-nitrogen bond lengths.
Notizen: Synthese und Struktur von 2,4,6,8-Tetrakis(diisopropylamino)- 2,4,6,8-tetrabora-tricyclo-[3.3.0.03,7]-octan Synthesis and Structure of 2,4,6,8-Tetrakis(diisopropylamino)- 2,4,6,8-tetrabora-tricyclo-[3.3.0.03,7]-octane
Authors: Krämer Albrecht , Pritzkow Hans , Siebert Walter
Published: March 2015

Dimerization of 1,2-bis(diisopropylamino)-1 ,2-dihydro-1,2-diborete (2) with palladium phthalocyanine quantitatively yields the eight-membered 1,2,5,6-tetrakis(diisopropylamino)-1,2,5,6-tetrahydro- 1,2,5,6-tetraborocine (3), which thermally or photolytically rearranges to give 2,4,6,8-tetrakis- (diisopropylamino)-2,4,6.8-tetrabora-tricyclo- [3,3,0,03,7]-octane (4). The X-ray structure analysis of the S4N4-like cage 4 exhibits long C-C-distances (1.67(1) Å ). 4 crystallizes in the space group F2dd with the lattice constants: a = 7.432(2), b = 24.802(6), c = 36.563(9) Å.
Notizen: Synthesis and Silica Gel Promoted Rearrangement of 5-Methylthio-3-carbo-t-butoxy-pent-3-en-2-one
Authors: Bałczewski Piotr , Mikołajczyk Marian
Published: March 2015

The title compound 3 obtained by the Knoevenagel condensation of t-butyl acetoacetate (1) with methylthioethanal (2) in the presence of zinc chloride was found to undergo an easy isomerization on silica gel to its β,γ-isomer which exists as a mixture of the keto (4) and enol (5) forms.
Synthese und Struktur von μ-Bromo-μ-dioxo-bis( phthalocyaninato-niob(V))tribromid, [(PcNb)2O2Br]+Br3
-, einem zweikernigen Phthalocyaninatokomplex / Synthesis and Structure of μ-Bromo-μ-dioxo-bis(phthalocyaninato-niobium(V))tribromide, [(PcNb)2O2Br]+Br3
-, a Dinuclear Phthalocyaninato Complex
Authors: Gingl Franz , Strähle Joachim
Published: March 2015

dioxo-bis(phthaIocyaninato-niob(V))tribromid, [(PcNb)20 2Br]+BrJ, einem zweikernigen Phthalocyaninatokomplex Synthesis and Structure of i w-Bromo-/ i/-dioxo-bis(phthalocyaninato-niobium(V))tribromide, [(PcNb)20 2Br]~Br3 , i w -Brom o-^-dioxo-bis(phthalocyaninato-niobium (V))tribrom ide. Synthesis. Crystal Structure
Photochemische Spaltung einer polaren Metall—Metall-Bindung durch Metall zu Metall Charge-Transfer-Anregung von [Ph3PAu—Co(CO)4] / Photochemical Splitting of a Polar Metal —Metal Bond by Metal to Metal Charge Transfer Excitation of [Ph3PAu—Co(CO)4]
Authors: Vogler Arnd , Kunkely Horst
Published: March 2015

Abstract The polar metal-metal bond of [Ph3PAu1-Co-1(CO)4] was cleaved photochemically by metal to metal (Co-1 ￫ Au+1) charge transfer excitation. Metallic gold, Ph3P, and [Co2(CO)8] were formed as products.
Öffnung von Dreikernclustern durch Diphosphinomethan-Liganden / Opening of Trinuclear Clusters by Diphosphinomethane Ligands
Authors: Planalp Roy P. , Vahrenkamp Heinrich
Published: March 2015

Abstract The phosphinidene bridged clusters FeCo2(CO)9(PMe) and FeCoWCp(CO)8(PM e) add the diphosphinomethane ligands dmpm and dppm with concomitant opening of two metal-metal bonds. The crystal structure determination of the addition product (Me2P-CH2-PMe2)FeCoWCp(CO)8(PMe) has shown that the Fe -W and Fe -Co bonds have been opened and the chelating diphosphine spans the Co -W bond. This is in contrast to the reaction with monodentate phosphines where the Co -W and Co -Fe bonds are broken. Upon heating the addition products eliminate two moles of CO with formation of the diphos­ phinom ethane substituted starting clusters, which in turn add CO under pressure to re-form the addition products.
Tris(benzoyl-thiobenzoyl-methanato-O,S)indium, a Conformer of a Facial Isomer
Authors: Gupta Vishnu D. , Mishra Anil K. , Nöth Heinrich , Polborn Kurt
Published: March 2015

Abstract A second modification o f the title com pound has been isolated and characterized by an X-ray structure analysis. It crystallizes in the monoclinic space group P21/c. The indium atom is hexacoordinated and surrounded by three sulfur and three oxygen atoms in a facial arrangement as has been found for a previously known isomer. However, the phenyl groups adopt a different orientation, hence it is a rotamer.
Ruthenium-Komplexe mit Diazadienen, IX. Ein neuartiger Chromophor aus zwei Diazadien-Ruthenium-Einheiten — Struktur und Eigenschaften von [(CO)2(DAD)CH3Ru- RuCH3(DAD)(CO)2] (DAD = ipr—N=CH—CH=N —ipr) / Ruthenium Complexes with Diazadienes, IX. A New Chromophore from Two Diazadiene Ruthenium Units — Structure and Properties of [(CO)2(DAD)CH3Ru -RuCH3(DAD)(CO)2] (DAD = ipr-N = CH -CH = N -ip r)
Authors: Dieck Heindirk tom , Rohde Wolfgang , Behrens Ulrich
Published: March 2015

The two-electron reduction of [(DAD)Ru(CO)2I2] (DAD = RN = CH -CH = NR ) gives the reactive ruthenates(O) [(DAD Ru(CO )2I]-, which add organic electrophiles to afford iodoruthenium organic com pounds such as [(DAD)Ru(CO)2(CH3)I] 3. Their electrochemical behaviour depends on the steric requirem ents of the D A D involved. With a small DAD (R = ipr) the oneelectron reduction gives a Ru(I) interm ediate, which finally yields a stable Ru-Ru-bonded dimer 4. With a bulky DAD(R - CH (ipr)2) the reduction proceeds to the organoruthenates [(DAD)Ru(CO)2R]-. The structure of the dimer 4 was determined by a single crystal X-rax diffraction study: C22H38N4O4Ru2 (624.69), space group F2dd, a = 9.944(2), b = 20.414(3), c = 27.644(5) Å , V = 5611,3(3) Å3, Z = 8; final R-value 0.034 from 2011 reflections. The molecule shows two almost planar (DAD )Ru(CO)2 units, which are staggered with respect to the Ru -Ru single bond. The methyl groups occupy the positions trans to this M-M bond. 4 represents a new type of chromophore with only one very intense and rather narrow absorption band near the infrared (λmax = 745 , ε = 30000 cm2 mmol-1), arising from the presence of a high-lying a-orbital, an antibonding combination of occupied d-orbitals and low-lying D A D π*-orbitals of proper symmetry.
Molecular and Crystal Structure of Two Cyclobuten-3,4-dione Derivatives: The Dithallium Salt of 1,2-Dicyanimino-(TI2CMCB) and the 1,2-Diiodocyclobuten-3,4-dione (I2CB)
Authors: Lunelli Bruno , Monari Magda
Published: March 2015

Abstract The crystal and molecular structure of the dithallium salt of the 1,2-dicyanim inocyclobuten-3,4-dione dianion and of 1,2-diiodocyclobuten-3,4-dione, determined by X-ray diffraction, are reported and discussed. Results of FT-IR and calorimetric measurements are also presented.
Zum dynamischen Strukturverhalten des Dimethylamin—Kohlendioxid-Komplexes (Dimcarb) / On the Dynamic Structure Behaviour of the Dimethylamine—Carbondioxide Complex (Dimcarb)
Authors: Radeglia Reiner , Andersch Jörg , Schroth Werner
Published: March 2015

Abstract Dimcarb, a liquid distillable 1 .8 :1-dimethylamine-carbondioxide complex which can be used as a preparatively profitable dimethylamine source, displays unusual properties in view of a salt ("dimethylammonium dimethylcarbamate"). The dynamic structure behaviour has been investigated by1'H, 13C, and 15N NMR spectroscopy: At ambient temperature dimcarb underlies a rapid dimethylamine change between ammonium and carbamate functionality (⊿G ≠ about 58 kJ/mol). On further temperature decreasing prototropic interactions between dimethylammonium and dimethylamine as well as dimethylcarbamate and dimethylcarbamic acid species are additionally revealed. Timely averaged, ionic structures predominate, obviously dimethylammonium dimethylcarbamate combinations as intimate ion pairs. Involved dimethylcarbamic acid can be trapped as methylester in high yield by reaction of dimcarb with diazomethane. Moreover, the dimethylcarbamic acid trimethylsilylester, obtained from dimcarb with the aid of trimethyl-chlorosilane, affords a crystalline product by methanolysis at -78 °C. probably dimethylcarbamic acid, which decomposes above -50 °C under carbondioxide elimination and regeneration of dimcarb.
Elementorganische Verbindungen mit o-Phenylenresten, XVI . 2:1-Komplexe von 2,3,7,8-Tetramethoxychalcogenanthrenen mit Tetracyanethen / Organometallic Compounds with o-Phenylene Substituents, Part XVI 2:1-Complexes of 2,3,7,8-Tetramethoxychalcogenanthrenes with Tetracyanoethene
Authors: Berges Peer , Kudnig Jens , Klar Günter , Martínez Enrique Sánchez , Calleja Ricardo Díaz
Published: March 2015

The CT complexes 2Vn2EE'·TCNE (1, E = E' = S; 2, E = E' = Se; 3, E = S, E' = Se) are prepared by combining the solutions of the components in acetonitrile. The three com pounds are isostructural and built up by Vn2EE'/TCNE/Vn2EE' units in which a TCNE molecule is inserted into the cavity formed by two of the folded, oppositely arranged Vn2EE' molecules. In this arrangement of donor and acceptor molecules an optimum overlap of the corresponding HOMOs and LUMOs is guaranteed as can be seen from the CNDOand HAM 3 calculations. The temperature dependence of the electrical conductivities shows the com pounds 1-3 to be semiconductors with gap energies of 1.27, 1.17 and 1.19 eV , resp.
Lithio-di-tert-butylfluorsilyl-tert-butylphosphan — Kristallstruktur und Reaktionen/Lithio-di-tert-butylfluorosilyl-tert-butylphosphane — Crystal Structure and Reactions
Authors: Andrianarison Mbolatiana , Klingebiel Uwe
Published: March 2015

Di-tert-butylfluorosilyl-tert-butylphosphane (1) reacts with n-C4H9Li to give the lithium salt (CMe3)2SiF-PLi(THF)3CMe3 (2) and butane. The crystal structure of 2 has been determined. Fluorosilylphosphanes of the type (CMe3)2SiFP(R)CMe3 [R = SiMe3 (5), SiCl2Me (6). SiCl3 (7), SiF2C6H5 (8), BFN (SiMe3)2 (9), SiClMeP(CMe3)SiF(CMe3)2 (10)] are obtained in the reaction of 2 with halogenosilanes and -borane. 6 and 7 undergo rearrangement via chloro-fluoro exchange reaction to give (CMe3)2SiCl-P(SiClRF)CMe3 [R = Cl (11), Me (12)].
Crystal Structure of a Binuclear Copper(II) Complex with μ-Alkoxo and μ-Pyridonato Bridges. Effect of the Dihedral Angle on the Superexchange Interaction
Authors: Nishida Yuzo , Masumoto Miyuki , Mori Yutaka
Published: March 2015

The crystal structure of the binuclear copper(II) complex. [Cu2(L)(2-pyridonato)] was determined by X-ray diffraction, where H3(L) represents the Schiff base ligand derived from 1,3-diaminopropane-2-ol and acetylacetone. Two copper(II) ions are bridged by alkoxide and 2-pyridonate groups with a Cu-Cu separation of 3.249(2) Å . Ferromagnetic interaction is found to be operating in this complex, which is attributed to the small dihedral angle (121°) between the two planes containing the copper(II) ion.
Spectral and Thermal Studies on Some New Anionic Mixed Alkyldithiocarbonato-Oxinato Transition Metal Complexes
Authors: Aly Aref A. M. , El-Said Asma I.
Published: March 2015

The preparation and characterization of some anionic mixed ligand com plexes of Co(II), Ni(II) and Cu(II) containing the two anionic ligands alkyldithiocarbonate and oxinate are reported. The ionic nature of the complexes was inferred from the conductivity data. Alkyldithiocarbonates act in these complexes as bidentate ligands. Based on the spectroscopic and magnetic data the complexes appear to possess pseudo-octahedral metal coordination.
Na4OI2 — ein neuer Alkalimetallchalkogenidhalogenid-Typ/Na4OI2 — a New Type of Alkali Metal Chalcogenide Halide
Authors: Sabrowsky Horst , Hippler Karin , Vogt Petra
Published: March 2015

The colourless compound Na4OI2: has been prepared and characterized by X-ray diffraction techniques. Na4OI2: crystallizes in a tetragonal body-centered lattice with a = 467.7(1) pm, c = 1602.0(3) pm (Z = 2) and is isotypic to K2NiF4.